Integrated methods for chemical synthesis

ABSTRACT

The integrated processes herein provide improved carbon efficiency for processes based on coal or biomass gasification or steam methane reforming. Provided are also ethylene oxide carbonylation products such as beta-propiolactone and succinic anhydride having a bio-based content between 0% and 100%, and methods for producing and analyzing the same.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/116,109, filed Feb. 13, 2015, which is incorporated herein byreference in its entirety.

FIELD

The present disclosure relates generally to the integrated production ofchemicals, and more specifically to integrated processes that provideimproved carbon efficiency for processes based on coal or biomassgasification or steam methane reforming. The present disclosure alsorelates to ethylene oxide carbonylation products, such asbeta-propiolactone and succinic anhydride having a bio-based content,and methods for producing and analyzing thereof.

BACKGROUND

Interest in finding sustainable methods to produce energy and chemicalscontinues to increase in the face of concerns that anthropogenic carbonemissions are responsible for global climate change. Among the optionsbeing considered is the use of biomass to feed chemical production viagasification. This process has appeal since the processes firstdeveloped more than a century ago for coal gasification can be appliedto practically any biomass input and the subsequent conversion of theresulting syngas to fuels and chemicals is a well-established processwith the potential to provide a diverse range of chemical products.

However, a drawback to gasification technology is that it is relativelyinefficient in terms of the percentage of the carbon input to thegasifier that is actually incorporated into end products. This is due inlarge part to the fact that coal and biomass-derived syngas has a low H₂to CO ratio (typically around ˜0.7) and must be upgraded by water gasshift reaction (WGSR) prior to utilization in downstream processes suchas Fischer Tropsch (FT) or methanol-to-olefins (MTO) synthesis thatrequires an H₂:CO ratio around 2. The water gas shift process consumes aportion of the carbon monoxide in the syngas releasing CO₂ and providingadditional hydrogen.

CO+H₂O⇄CO₂+H₂

The resulting CO₂ (22 kg CO₂ per kg of H₂ produced) is emitted to theatmosphere and erodes the carbon efficiency and environmental benefit ofbiomass gasification technologies.

A related situation exists for conversion of carbonaceous feedstocks toproduce pure hydrogen streams for use in chemical production (e.g.,ammonia production) or for use as a fuel. Here, the preferred process ismethane steam reforming (MSR): CH₄+H₂O ⇄CO+3H₂. Again, the gas streamproduced by MSR is typically treated by WGSR to increase the hydrogencontent resulting in CO₂ emissions.

Typical routes to C3 and C4 chemicals require that all of the carbonatoms in the molecules produced be derived wholly from either bio-basedor fossil sources. Accordingly, there is also a need for methods ofproducing chemicals such as beta-propiolactone (BPL) and succinicanhydride (SA) in such a way that they contain a known and controllablecontent of bio-based materials. Furthermore, existing methods used toproduce bio-based BPL and SA at scale rely on the availability ofbio-based supplies of C3 feedstocks such as propene, which are noteconomically competitive with fossil sources.

It is also a challenge to determine which feedstocks were used toproduce a given batch of beta-propiolactone or succinic anhydride, asonce the chemicals are produced, any sample of BPL or SA is largelyindistinguishable. Standards bodies, secondary manufacturers, and endconsumers are increasingly concerned with the source of the productsthey use, and particularly the bio-based content of the chemicals usedto make those products. Accordingly, methods for determining thebio-based content of the chemicals used to produce BPL, SA, and theirdownstream products are needed.

BRIEF SUMMARY

The methods and systems described herein address the various challengesknown in the art with respect to producing various bio-based chemicals.For example, epoxide carbonylation can be performed industriallyutilizing syngas streams containing hydrogen, carbon monoxide andvarying amounts carbon dioxide. However, contrary to expectation, theepoxide carbonylation reaction proceeds selectively in the presence ofthese mixed gas streams and incorporates excess CO from the syngasstream into valuable chemical precursors. This is economically andenvironmentally preferable to performing WGSR which releases the excesscarbon as CO₂. The integrated processes herein therefore provideimproved carbon efficiency for processes based on coal or biomassgasification or steam methane reforming.

In one aspect, provided is an integrated process for the conversion ofbiomass or coal to FT products and commodity chemicals derived fromepoxide carbonylation. In certain embodiments, such methods comprise:

a) in a first reaction zone, contacting syngas derived from gasificationof biomass or coal with an epoxide in the presence of a carbonylationcatalyst thereby consuming carbon monoxide from the syngas and producingan epoxide carbonylation product,

b) recovering an upgraded gas stream from the first reaction zonewherein the upgraded gas stream has a higher hydrogen to carbon monoxideratio than the starting syngas stream,

c) in a second reaction zone, utilizing the upgraded gas stream toconduct a second chemical process requiring a hydrogen to carbonmonoxide ratio higher than the ratio in the industrial gas streamutilized in step (a).

In certain embodiments of the method above, the second chemical processcomprises Fischer Tropsch synthesis.

In a second aspect, provided is an integrated process for the productionof hydrogen and commodity chemicals derived from epoxide carbonylation.In certain embodiments, such methods comprise:

a) in a first reaction zone, contacting a syngas stream derived frommethane steam reforming with an epoxide in the presence of acarbonylation catalyst thereby consuming carbon monoxide from the syngasstream and producing an epoxide carbonylation product,

b) recovering an upgraded gas stream from the first reaction zonewherein the upgraded gas stream has a higher hydrogen to carbon monoxideratio than the starting syngas stream, and

c) in a second reaction zone, utilizing the upgraded gas stream toconduct a second chemical process requiring a hydrogen to carbonmonoxide ratio higher than the ratio in the industrial gas streamutilized in step (a).

In certain embodiments, the epoxide carbonylation product produced instep (a) of the methods above is selected from the group consisting of:optionally substituted beta propiolactone, optionally substitutedsuccinic anhydride, and optionally substituted polypropiolactone. Incertain embodiments, the epoxide in the methods above is ethylene oxideand the epoxide carbonylation product is selected from the groupconsisting of: beta propiolactone (BPL), succinic anhydride (SA), andpolypropiolactone (PPL). In certain embodiments, the epoxide in themethods above is propylene oxide and the epoxide carbonylation productis selected from the group consisting of: beta butyrolactone, methylsuccinic anhydride and poly(3-hydroxy butyrate).

In certain embodiments of the methods above, the syngas stream in step(a) is characterized in that it has an H₂ to CO ratio less than 1.2. Incertain embodiments, the upgraded gas stream in step (b) ischaracterized in that it has an H₂ to CO ratio greater than 1.9.

In another aspect, provided is an integrated process for the productionof hydrogen and commodity chemicals derived from beta lactonecarbonylation. In certain embodiments, such methods comprise:

a) in a first reaction zone, contacting syngas with a beta propiolactonein the presence of a carbonylation catalyst thereby consuming carbonmonoxide from the syngas and producing a succinic anhydride product,

b) recovering an upgraded gas stream from the first reaction zonewherein the upgraded gas stream has a higher hydrogen to carbon monoxideratio than the starting syngas stream,

c) in a second reaction zone, utilizing the upgraded gas stream toconduct a second chemical process requiring a hydrogen to carbonmonoxide ratio higher than the ratio in the industrial gas streamutilized in step (a).

In certain embodiments of this aspect, the syngas in step (a) is derivedfrom methane steam reforming (MSR). In certain embodiments, the syngasin step (a) is an upgraded gas stream produced as described in the firsttwo aspects of the methods described above.

In certain embodiments of this aspect, the beta propiolactonecarbonylation reaction zone is operated under conditions such thatsubstantially all of the CO in the syngas stream is consumed.

In some embodiments, provided are ethylene oxide carbonylation products(such as BPL and SA), produced by carbonylation of ethylene oxidewherein the bio-based content of the ethylene carbonylation products arebetween 0% and 100% (non-inclusive).

In some embodiments, provided is a process for producing ethylene oxidecarbonylation products (such as BPL and SA) having a bio-based contentgreater than 0% and less than 100%, comprising carbonylating ethyleneoxide using carbon monoxide, wherein one of the ethylene oxide andcarbon monoxide has a bio-based content greater than 0%, and the otherhas a bio-based content of less than 100%.

In some embodiments, provided is a method for determining whether asample of BPL was produced from a combination of bio-based and fossilcarbon synthons, comprising thermally decomposing the BPL to ethyleneand carbon dioxide; determining the isotopic abundance of ¹⁴C in thecarbon dioxide carbon; and determining the isotopic abundance of ¹⁴C inthe ethylene carbons.

In some embodiments, provided is a method for determining whether asample of SA was produced from a combination of bio-based and fossilcarbon synthons, comprising thermally decomposing the SA toγ-ketopimelic acid and carbon dioxide; determining the isotopicabundance of ¹⁴C in the carbon dioxide carbon; and determining theisotopic abundance of ¹⁴C in the γ-ketopimelic acid carbons.

In some embodiments, provided is a method for determining whether asample of polyacrylic acid (PAA) was produced from a combination ofbio-based and fossil carbon synthons, comprising thermally decomposingthe PAA in the presence of a catalyst to carbon dioxide and a residue;determining the isotopic abundance of ¹⁴C in the carbon dioxide, anddetermining the isotopic abundance of ¹⁴C in the residue.

In some aspects, provided is beta-propiolactone produced bycarbonylation of ethylene oxide having a pMC of zero, as defined by ASTMD6866, using carbon monoxide having a pMC greater than zero, as definedby ASTM D6866. In other aspects, provided is beta-propiolactone producedby carbonylation of ethylene oxide having a pMC greater than zero, asdefined by ASTM D6866, using carbon monoxide having a pMC of zero, asdefined by ASTM D6866. In certain aspects, provided isbeta-propiolactone produced by carbonylation of ethylene oxide usingcarbon monoxide, wherein one of the ethylene oxide and carbon monoxidehas a biobased content greater than zero percent, and the other has abiobased content of less than 100 percent. In some variations, providedis beta propiolactone, wherein two of the three carbon atoms in the betapropiolactone are bio-based and the third carbon atom is fossil-based.In other aspects, provided is beta propiolactone, wherein one of thethree carbon atoms in the beta propiolactone is bio-based and the othertwo carbons atom are fossil-based.

In other aspects, provided is succinic anhydride produced bycarbonylation of ethylene oxide having a pMC greater than zero, asdefined by ASTM D6866, using carbon monoxide having a pMC of zero, asdefined by ASTM D6866. In other aspects, provided is Succinic anhydrideproduced by carbonylation of ethylene oxide using carbon monoxide,wherein one of the ethylene oxide and carbon monoxide has a biobasedcontent greater than zero percent, and the other has a biobased contentof less than 100 percent. In some variations, provided is succinicanhydride, wherein two of the four carbon atoms of the succinicanhydride are bio-based and two of the carbon atoms are fossil-based.

BRIEF DESCRIPTION OF THE FIGURES

The present application can be best understood by reference to thefollowing description taken in conjunction with the accompanyingfigures, in which like parts may be referred to by like numerals.

FIG. 1 shows a schematic of an exemplary integrated process for theconversion of biomass or coal to synthesis gas and commodity chemicalsor polymers derived from epoxide carbonylation.

FIG. 2 shows a schematic of an exemplary integrated hydrogen productionprocess.

FIG. 3 shows a schematic of an alternate exemplary process production ofhydrogen and commodity chemicals derived from beta lactonecarbonylation.

FIG. 4 shows a schematic of an exemplary process utilizing twocarbonylation stages.

FIG. 5 shows a schematic of an exemplary process for the production ofacrylic acid from biomass.

FIG. 6 shows a schematic of an exemplary process for the production ofC4 chemicals from biomass.

FIG. 7 shows a schematic of an exemplary process for the production ofBPL and related products from both bio-based and fossil sources.

DEFINITIONS

Definitions of specific functional groups and chemical terms aredescribed in more detail below. The chemical elements are identified inaccordance with the Periodic Table of the Elements, CAS version,Handbook of Chemistry and Physics, 75^(th) Ed., inside cover, andspecific functional groups are generally defined as described therein.Additionally, general principles of organic chemistry, as well asspecific functional moieties and reactivity, are described in OrganicChemistry, Thomas Sorrell, University Science Books, Sausalito, 1999;Smith and March March's Advanced Organic Chemistry, 5^(th) Edition, JohnWiley & Sons, Inc., New York, 2001; Larock, Comprehensive OrganicTransformations, VCH Publishers, Inc., New York, 1989; Carruthers, SomeModern Methods of Organic Synthesis, 3^(rd) Edition, CambridgeUniversity Press, Cambridge, 1987.

Certain compounds herein can comprise one or more asymmetric centers,and thus can exist in various stereoisomeric forms, e.g., enantiomersand/or diastereomers. Thus, compounds and compositions thereof may be inthe form of an individual enantiomer, diastereomer or geometric isomer,or may be in the form of a mixture of stereoisomers. In certainembodiments, the compounds herein are enantiopure compounds. In certainother embodiments, mixtures of enantiomers or diastereomers areprovided.

Furthermore, certain compounds, as described herein may have one or moredouble bonds that can exist as either a Z or E isomer, unless otherwiseindicated. In some variations, the compounds include individual isomerssubstantially free of other isomers and alternatively, as mixtures ofvarious isomers, e.g., racemic mixtures of enantiomers. In addition tothe above-mentioned compounds per se, provided are also compositionscomprising one or more compounds.

As used herein, the term “isomers” includes any and all geometricisomers and stereoisomers. For example, “isomers” include cis- andtrans-isomers, E- and Z-isomers, R- and S-enantiomers, diastereomers,(D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixturesthereof, as falling within the scope herein. For instance, a compoundmay, in some embodiments, be provided substantially free of one or morecorresponding stereoisomers, and may also be referred to as“stereochemically enriched.”

Where a particular enantiomer is preferred, it may, in some embodimentsbe provided substantially free of the opposite enantiomer, and may alsobe referred to as “optically enriched.” “Optically enriched,” as usedherein, means that the compound is made up of a significantly greaterproportion of one enantiomer. In certain embodiments the compound ismade up of at least about 90% by weight of an enantiomer. In someembodiments the compound is made up of at least about 95%, 97%, 98%,99%, 99.5%, 99.7%, 99.8%, or 99.9% by weight of an enantiomer. In someembodiments the enantiomeric excess of provided compounds is at leastabout 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9%. In someembodiments, enantiomers may be isolated from racemic mixtures by anymethod known to those skilled in the art, including chiral high pressureliquid chromatography (HPLC) and the formation and crystallization ofchiral salts or prepared by asymmetric syntheses. See, for example,Jacques, et al., Enantiomers, Racemates and Resolutions (WileyInterscience, New York, 1981); Wilen, S. H., et al., Tetrahedron 33:2725(1977); Eliel, E. L. Stereochemistry of Carbon Compounds (McGraw-Hill,NY, 1962); Wilen, S. H. Tables of Resolving Agents and OpticalResolutions p. 268 (E. L. Eliel, Ed., Univ. of Notre Dame Press, NotreDame, Ind. 1972).

The terms “halo” and “halogen” as used herein refer to an atom selectedfrom fluorine (fluoro, —F), chlorine (chloro, —Cl), bromine (bromo,—Br), and iodine (iodo, —I).

The term “aliphatic” or “aliphatic group”, as used herein, denotes ahydrocarbon moiety that may be straight-chain (i.e., unbranched),branched, or cyclic (including fused, bridging, and spiro-fusedpolycyclic) and may be completely saturated or may contain one or moreunits of unsaturation, but which is not aromatic. In some variations,the aliphatic group is unbranched or branched. In other variations, thealiphatic group is cyclic. Unless otherwise specified, in somevariations, aliphatic groups contain 1-30 carbon atoms. In certainembodiments, aliphatic groups contain 1-12 carbon atoms. In certainembodiments, aliphatic groups contain 1-8 carbon atoms. In certainembodiments, aliphatic groups contain 1-6 carbon atoms. In someembodiments, aliphatic groups contain 1-5 carbon atoms, in someembodiments, aliphatic groups contain 1-4 carbon atoms, in yet otherembodiments aliphatic groups contain 1-3 carbon atoms, and in yet otherembodiments aliphatic groups contain 1-2 carbon atoms. Suitablealiphatic groups include, for example, linear or branched, alkyl,alkenyl, and alkynyl groups, and hybrids thereof such as(cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

The term “heteroaliphatic,” as used herein, refers to aliphatic groupswherein one or more carbon atoms are independently replaced by one ormore atoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, or boron. In certain embodiments, one or twocarbon atoms are independently replaced by one or more of oxygen,sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may besubstituted or unsubstituted, branched or unbranched, cyclic or acyclic,and include “heterocycle,” “hetercyclyl,” “heterocycloaliphatic,” or“heterocyclic” groups. In some variations, the heteroaliphatic group isbranched or unbranched. In other variations, the heteroaliphatic groupis cyclic. In yet other variations, the heteroaliphatic group isacyclic.

In some variations, the term “epoxide”, as used herein, refers to asubstituted or unsubstituted oxirane. Substituted oxiranes includemonosubstituted oxiranes, disubstituted oxiranes, trisubstitutedoxiranes, and tetrasubstituted oxiranes. Such epoxides may be furtheroptionally substituted as defined herein. In certain embodiments,epoxides comprise a single oxirane moiety. In certain embodiments,epoxides comprise two or more oxirane moieties.

In some variations, the term “glycidyl”, as used herein, refers to anoxirane substituted with a hydroxyl methyl group or a derivativethereof. In other variations, the term glycidyl as used herein is meantto include moieties having additional substitution on one or more of thecarbon atoms of the oxirane ring or on the methylene group of thehydroxymethyl moiety, examples of such substitution may include, forexample, alkyl groups, halogen atoms, and aryl groups. The termsglycidyl ester, glycidyl acrylate, and glycidyl ether denotesubstitution at the oxygen atom of the above-mentioned hydroxymethylgroup. For example, the oxygen atom is bonded to an acyl group, anacrylate group, or an alkyl group respectively.

The term “acrylate” or “acrylates” as used herein refer to any acylgroup having a vinyl group adjacent to the acyl carbonyl. The termsencompass mono-, di- and tri-substituted vinyl groups. Acrylates mayinclude, for example, acrylate, methacrylate, ethacrylate, cinnamate(3-phenylacrylate), crotonate, tiglate, and senecioate.

The term “polymer”, as used herein, refers to a molecule comprisingmultiple repeating units. In some variations, the polymer is a moleculeof high relative molecular mass, the structure of which comprises themultiple repetition of units derived, actually or conceptually, frommolecules of low relative molecular mass. In certain embodiments, apolymer is comprised of only one monomer species (e.g., polyethyleneoxide). In certain embodiments, the polymer may be a copolymer,terpolymer, heteropolymer, block copolymer, or tapered heteropolymer ofone or more epoxides. In one variation, the polymer may be a copolymer,terpolymer, heteropolymer, block copolymer, or tapered heteropolymer oftwo or more monomers.

The term “unsaturated”, as used herein, means that a moiety has one ormore double or triple bonds.

The terms “cycloaliphatic”, “carbocycle”, or “carbocyclic”, used aloneor as part of a larger moiety, refer to a saturated or partiallyunsaturated cyclic aliphatic monocyclic, bicyclic, or polycyclic ringsystems, as described herein, having from 3 to 12 members, wherein thealiphatic ring system is optionally substituted as defined above anddescribed herein. Cycloaliphatic groups include, for example,cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl,cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, andcyclooctadienyl. In some embodiments, the cycloalkyl has 3-6 carbons.The terms “cycloaliphatic”, “carbocycle” or “carbocyclic” also includealiphatic rings that are fused to one or more aromatic or nonaromaticrings, such as decahydronaphthyl or tetrahydronaphthyl, where theradical or point of attachment is on the aliphatic ring. In someembodiments, a carbocyclic group is bicyclic. In some embodiments, acarbocyclic group is tricyclic. In some embodiments, a carbocyclic groupis polycyclic.

The term “alkyl,” as used herein, refers to a saturated hydrocarbonradical. In some variations, the alkyl group is a saturated, straight-or branched-chain hydrocarbon radicals derived from an aliphatic moietycontaining between one and six carbon atoms by removal of a singlehydrogen atom. Unless otherwise specified, in some variations, alkylgroups contain 1-12 carbon atoms. In certain embodiments, alkyl groupscontain 1-8 carbon atoms. In certain embodiments, alkyl groups contain1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5 carbonatoms, in some embodiments, alkyl groups contain 1-4 carbon atoms, inyet other embodiments alkyl groups contain 1-3 carbon atoms, and in yetother embodiments alkyl groups contain 1-2 carbon atoms. Alkyl radicalsmay include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl,iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl,neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl,and dodecyl.

The term “alkenyl,” as used herein, denotes a monovalent group having atleast one carbon-carbon double bond. In some variations, the alkenylgroup is a monovalent group derived from a straight- or branched-chainaliphatic moiety having at least one carbon-carbon double bond by theremoval of a single hydrogen atom. Unless otherwise specified, in somevariations, alkenyl groups contain 2-12 carbon atoms. In certainembodiments, alkenyl groups contain 2-8 carbon atoms. In certainembodiments, alkenyl groups contain 2-6 carbon atoms. In someembodiments, alkenyl groups contain 2-5 carbon atoms, in someembodiments, alkenyl groups contain 2-4 carbon atoms, in yet otherembodiments alkenyl groups contain 2-3 carbon atoms, and in yet otherembodiments alkenyl groups contain 2 carbon atoms. Alkenyl groupsinclude, for example, ethenyl, propenyl, butenyl, and1-methyl-2-buten-1-yl.

The term “alkynyl,” as used herein, refers to a monovalent group havingat least one carbon-carbon triple bond. In some variations, the alkynylgroup is a monovalent group derived from a straight- or branched-chainaliphatic moiety having at least one carbon-carbon triple bond by theremoval of a single hydrogen atom. Unless otherwise specified, in somevariations, alkynyl groups contain 2-12 carbon atoms. In certainembodiments, alkynyl groups contain 2-8 carbon atoms. In certainembodiments, alkynyl groups contain 2-6 carbon atoms. In someembodiments, alkynyl groups contain 2-5 carbon atoms, in someembodiments, alkynyl groups contain 2-4 carbon atoms, in yet otherembodiments alkynyl groups contain 2-3 carbon atoms, and in yet otherembodiments alkynyl groups contain 2 carbon atoms. Representativealkynyl groups include, for example, ethynyl, 2-propynyl (propargyl),and 1-propynyl.

The term “carbocycle” and “carbocyclic ring” as used herein, refers tomonocyclic and polycyclic moieties wherein the rings contain only carbonatoms. Unless otherwise specified, carbocycles may be saturated,partially unsaturated or aromatic, and contain 3 to 20 carbon atoms.Representative carbocyles include, for example, cyclopropane,cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2,1]heptane,norbornene, phenyl, cyclohexene, naphthalene, and spiro[4.5]decane.

The term “aryl” used alone or as part of a larger moiety as in“aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic andpolycyclic ring systems having a total of five to 20 ring members,wherein at least one ring in the system is aromatic and wherein eachring in the system contains three to twelve ring members. The term“aryl” may be used interchangeably with the term “aryl ring”. In certainembodiments, “aryl” refers to an aromatic ring system which includes,for example, phenyl, naphthyl, and anthracyl, which may bear one or moresubstituents. Also included within the scope of the term “aryl”, as itis used herein, is a group in which an aromatic ring is fused to one ormore additional rings, such as benzofuranyl, indanyl, phthalimidyl,naphthimidyl, phenanthridinyl, and tetrahydronaphthyl.

The terms “heteroaryl” and “heteroar-”, used alone or as part of alarger moiety, e.g., “heteroaralkyl”, or “heteroaralkoxy”, refer togroups having 5 to 14 ring atoms, preferably 5, 6, 9 or 10 ring atoms;having 6, 10, or 14 pi (π) electrons shared in a cyclic array; andhaving, in addition to carbon atoms, from one to five heteroatoms. Theterm “heteroatom” refers to nitrogen, oxygen, or sulfur, and includesany oxidized form of nitrogen or sulfur, and any quaternized form of abasic nitrogen. Heteroaryl groups include, for example, thienyl,furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl,purinyl, naphthyridinyl, benzofuranyl and pteridinyl. The terms“heteroaryl” and “heteroar-”, as used herein, also include groups inwhich a heteroaromatic ring is fused to one or more aryl,cycloaliphatic, or heterocyclyl rings, where the radical or point ofattachment is on the heteroaromatic ring. Examples include indolyl,isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl,benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl,phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl,acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl,tetrahydroquinolinyl, tetrahydroisoquinolinyl, andpyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be mono- orbicyclic. The term “heteroaryl” may be used interchangeably with theterms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any ofwhich terms include rings that are optionally substituted. The term“heteroaralkyl” refers to an alkyl group substituted by a heteroaryl,wherein the alkyl and heteroaryl portions independently are optionallysubstituted.

As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclicradical”, and “heterocyclic ring” are used interchangeably and may besaturated or partially unsaturated, and have, in addition to carbonatoms, one or more, preferably one to four, heteroatoms, as definedabove. In some variations, the heterocyclic group is a stable 5- to7-membered monocyclic or 7- to 14-membered bicyclic heterocyclic moietythat is either saturated or partially unsaturated, and having, inaddition to carbon atoms, one or more, preferably one to four,heteroatoms, as defined above. When used in reference to a ring atom ofa heterocycle, the term “nitrogen” includes a substituted nitrogen. Asan example, in a saturated or partially unsaturated ring having 0-3heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen maybe N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or ⁺NR(as in N-substituted pyrrolidinyl).

A heterocyclic ring can be attached to its pendant group at anyheteroatom or carbon atom that results in a stable structure and any ofthe ring atoms can be optionally substituted. Examples of such saturatedor partially unsaturated heterocyclic radicals include, for example,tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl,piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl,decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl,diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. Theterms “heterocycle”, “heterocyclyl”, “heterocyclyl ring”, “heterocyclicgroup”, “heterocyclic moiety”, and “heterocyclic radical”, are usedinterchangeably herein, and also include groups in which a heterocyclylring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings,such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl, ortetrahydroquinolinyl, where the radical or point of attachment is on theheterocyclyl ring. A heterocyclyl group may be mono- or bicyclic. Theterm “heterocyclylalkyl” refers to an alkyl group substituted by aheterocyclyl, wherein the alkyl and heterocyclyl portions independentlyare optionally substituted.

As used herein, the term “partially unsaturated” refers to a ring moietythat includes at least one double or triple bond. The term “partiallyunsaturated” is intended to encompass rings having multiple sites ofunsaturation, but is not intended to include aryl or heteroarylmoieties, as herein defined.

As described herein, compounds described herein may contain “optionallysubstituted” moieties. In general, the term “substituted”, whetherpreceded by the term “optionally” or not, means that one or morehydrogens of the designated moiety are replaced with a suitablesubstituent. Unless otherwise indicated, an “optionally substituted”group may have a suitable substituent at each substitutable position ofthe group, and when more than one position in any given structure may besubstituted with more than one substituent selected from a specifiedgroup, the substituent may be either the same or different at everyposition. Combinations of substituents envisioned herein are preferablythose that result in the formation of stable or chemically feasiblecompounds. The term “stable”, as used herein, refers to compounds thatare not substantially altered when subjected to conditions to allow fortheir production, detection, and, in certain embodiments, theirrecovery, purification, and use for one or more of the purposesdisclosed herein.

In some chemical structures herein, substituents are shown attached to abond which crosses a bond in a ring of the depicted molecule. This meansthat one or more of the substituents may be attached to the ring at anyavailable position (usually in place of a hydrogen atom of the parentstructure). In cases where an atom of a ring so substituted has twosubstitutable positions, two groups may be present on the same ringatom. When more than one substituent is present, each is definedindependently of the others, and each may have a different structure. Incases where the substituent shown crossing a bond of the ring is —R,this has the same meaning as if the ring were said to be “optionallysubstituted” as described in the preceding paragraph.

Suitable monovalent substituents on a substitutable carbon atom of an“optionally substituted” group are independently halogen;—(CH₂)₀₋₄R^(o); —(CH₂)₀₋₄OR^(o); —O—(CH₂)₀₋₄C(O)OR^(o);—(CH₂)₀₋₄CH(OR^(o))₂; —(CH₂)₀₋₄SR^(o); —(CH₂)₀₋₄Ph, which may besubstituted with R^(o); —(CH₂)₀₋₄O(CH₂)₀₋₁Ph which may be substitutedwith R^(o); —CH═CHPh, which may be substituted with R^(o); —NO₂; —CN;—N₃; —(CH₂)₀₋₄N(R^(o))₂; —(CH₂)₀₋₄N(R^(o))C(O)R^(o); —N(R^(o))C(S)R^(o);—(CH₂)₀₋₄N(R^(o)C(O)NR^(o))₂; —N(R^(o)C(S)NR^(o) ₂;—(CH₂)₀₋₄N(R^(o)C(O)OR^(o); —N(R^(o))N(R^(o))C(O)R^(o);—N(R^(o))N(R^(o))C(O)NR^(o) ₂; —N(R^(o))N(R^(o))C(O)OR^(o);—(CH₂)₀₋₄C(O)R^(o); —C(S)R^(o); —(CH₂)₀₋₄C(O)OR^(o);—(CH₂)₀₋₄C(O)N(R^(o))₂; —(CH₂)₀₋₄C(O)SR^(o); —(CH₂)₀₋₄C(O)OSiR^(o) ₃;—(CH₂)₀₋₄OC(O)R^(o); —OC(O)(CH₂)₀₋₄SR^(o), —SC(S)SR^(o);—(CH₂)₀₋₄SC(O)R^(o); —(CH₂)₀₋₄C(O)NR^(o) ₂; —C(S)NR^(o) ₂; —C(S)SR^(o);—SC(S)SR^(o), —(CH₂)₀₋₄OC(O)NR^(o) ₂; —C(O)N(OR^(o))R^(o);—C(O)C(O)R^(o); —C(O)CH₂C(O)R^(o); —C(NOR^(o))R^(o); —(CH₂)₀₋₄SSR^(o);—(CH₂)₀₋₄S(O)₂R^(o); —(CH₂)₀₋₄S(O)₂OR^(o); —(CH₂)₀₋₄OS(O)₂R^(o);—S(O)₂NR^(o) ₂; —(CH₂)₀₋₄S(O)R^(o); —N(R^(o))S(O)₂NR^(o) ₂;—N(R^(o))S(O)₂R^(o); —N(OR^(o))R^(o); —C(NH)NR^(o) ₂; —P(O)₂R^(o);—P(O)R^(o) ₂; —OP(O)R^(o) ₂, —OP(O)(OR^(o))₂; SiR^(o) ₃; —(C₁₋₄ straightor branched)alkylene)O—N(R^(o))₂; or —(C₁₋₄ straight orbranched)alkylene)C(O)O—N(R^(o))₂, wherein each R^(o) may be substitutedas defined below and is independently hydrogen, C₁₋₈ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, and sulfur, or, notwithstanding the definition above, twoindependent occurrences of R^(o), taken together with their interveningatom(s), form a 3-12-membered saturated, partially unsaturated, or arylmono- or polycyclic ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, and sulfur, which may be substituted as definedbelow.

Suitable monovalent substituents on R^(o) (or the ring formed by takingtwo independent occurrences of R^(o) together with their interveningatoms), are independently halogen, —(CH₂)₀₋₂R^(•), -(haloR^(•)),—(CH₂)₀₋₂OH, —(CH₂)₀₋₂OR^(•), —(CH₂)₀₋₂CH(OR^(•))₂; —O(haloR^(•)), —CN,—N₃, —(CH₂)₀₋₂C(O)R^(•), —(CH₂)₀₋₂C(O)OH, —(CH₂)₀₋₂C(O)OR^(•),—(CH₂)₀₋₄C(O)N(R^(o))₂; —(CH₂)₀₋₂SR^(•), —(CH₂)₀₋₂SH, —(CH₂)₀₋₂NH₂,—(CH₂)₀₋₂NHR^(•), —(CH₂)₀₋₂NR^(•) ₂, —NO₂, —SiR^(•) ₃, —OSiR^(•) ₃,—C(O)SR^(•), —(C₁₋₄ straight or branched alkylene)C(O)OR^(•), or—SSR^(•) wherein each R^(•) is unsubstituted or where preceded by “halo”is substituted only with one or more halogens, and is independentlyselected from C₁₋₄ aliphatic, —CH₂Ph, —O(CH₂)₀₋₁Ph, or a 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, and sulfur. Suitabledivalent substituents on a saturated carbon atom of R^(o) include ═O and═S.

Suitable divalent substituents on a saturated carbon atom of an“optionally substituted” group include the following: ═O, ═S, ═NNR*₂,═NNHC(O)R*, ═NNHC(O)OR*, ═NNHS(O)₂R*, ═NR*, ═NOR*, —O(C(R^(*) ₂))₂₋₃O—,or —S(C(R*₂))₂₋₃S—, wherein each independent occurrence of R* isselected from hydrogen, C₁₋₆ aliphatic which may be substituted asdefined below, or an unsubstituted 5-6-membered saturated, partiallyunsaturated, or aryl ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, and sulfur. Suitable divalent substituents thatare bound to vicinal substitutable carbons of an “optionallysubstituted” group include: —O(CR*₂)₂₋₃O—, wherein each independentoccurrence of R* is selected from hydrogen, C₁₋₆ aliphatic which may besubstituted as defined below, or an unsubstituted 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, and sulfur.

Suitable substituents on the aliphatic group of R* include halogen,—R^(•), -(haloR^(•)), —OH, —OR^(•), —O(haloR^(•)), —CN, —C(O)OH,—C(O)OR^(•), —NH₂, —NHR^(•), —NR^(•) ₂, or —NO₂, wherein each R^(•) isunsubstituted or where preceded by “halo” is substituted only with oneor more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, and sulfur.

Suitable substituents on a substitutable nitrogen of an “optionallysubstituted” group include —R^(†), —NR^(†) ₂, —C(O)R^(†), —C(O)OR^(†),—C(O)C(O)R^(†), —C(O)CH₂C(O)R^(†), —S(O)₂R^(†), —S(O)₂NR^(†) ₂,—C(S)NR^(†) ₂, —C(NH)NR^(†) ₂, or —N(R^(†))S(O)₂R^(†); wherein eachR^(†) is independently hydrogen, C₁₋₆ aliphatic which may be substitutedas defined below, unsubstituted —OPh, or an unsubstituted 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, and sulfur, or,notwithstanding the definition above, two independent occurrences ofR^(†), taken together with their intervening atom(s) form anunsubstituted 3-12-membered saturated, partially unsaturated, or arylmono- or bicyclic ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, and sulfur.

Suitable substituents on the aliphatic group of R^(†) are independentlyhalogen, —R^(•), (haloR^(•)), —OH, —OR^(•), —O(haloR^(•)), —CN, —C(O)OH,—C(O)OR^(•), —NH₂, —NHR^(•), —NR^(•) ₂, or —NO₂, wherein each R^(•) isunsubstituted or where preceded by “halo” is substituted only with oneor more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, and sulfur.

As used herein, the term “catalyst” refers to a substance the presenceof which increases the rate of a chemical reaction, while not beingconsumed or undergoing a permanent chemical change itself.

“Tetradentate” refers to ligands having four sites capable ofcoordinating to a single metal center.

As used herein, the term “about” preceding one or more numerical valuesmeans the numerical value±5%. t should be understood that reference to“about” a value or parameter herein includes (and describes) embodimentsthat are directed to that value or parameter per se. For example,description referring to “about x” includes description of “x” per se.

DETAILED DESCRIPTION

In certain aspects, provided are integrated processes that enablesimultaneous production of valuable chemicals or polymers whileupgrading synthesis gas by increasing the hydrogen to carbon monoxideratio in the gas. The processes described herein represent significanteconomic and environmental improvements versus prior art methodsutilizing the water gas shift reaction which relies on conversion of COto waste CO₂ to increase the hydrogen ratio. The integrated processesherein provide improved carbon efficiency for processes based on coal orbiomass gasification or steam methane reforming.

In a first aspect, provided are integrated processes for the conversionof biomass or coal to synthesis gas and commodity chemicals or polymersderived from epoxide carbonylation. In certain embodiments, such methodscomprise:

a) in a first reaction zone, contacting syngas derived from gasificationof biomass or coal with an epoxide in the presence of a carbonylationcatalyst thereby consuming carbon monoxide from the syngas and producingan epoxide carbonylation product,

b) recovering an upgraded gas stream from the first reaction zonewherein the upgraded gas stream has a higher hydrogen to carbon monoxideratio than the starting syngas stream, and

c) in a second reaction zone, utilizing the upgraded gas stream toconduct a second chemical process requiring a hydrogen to carbonmonoxide ratio higher than the ratio in the industrial gas streamutilized in step (a).

A schematic of an exemplary process is shown in FIG. 1. The processbegins with a gasifier unit which converts biomass, coal or othercarbonaceous feedstocks into a synthesis gas stream 101. Gas stream 101is directed to carbonylation reactor 200 where it is brought intocontact with an epoxide (fed to reactor 200 via stream 201). In reactor200, the epoxide and carbon monoxide in the syngas stream react in thepresence of a carbonylation catalyst to produce epoxide carbonylationproducts which are ultimately recovered via product stream P1. Ahydrogen-enriched syngas stream 102 is recovered from reactor 200 andfed to reactor 300 where it is consumed as the feedstock for FischerTropsch synthesis yielding FT products via product stream P2. FIG. 1also illustrates the prior art process wherein water gas shift reactor400 is utilized in place of carbonylation reactor 200. In this case, COin the synthesis gas stream 101 is converted to CO₂ and hydrogen in theusual fashion with CO₂ exiting via waste stream W1.

In a second aspect, provided are integrated processes for the conversionof methane into hydrogen. In certain embodiments, such methods comprise:

a) in a first reaction zone, contacting a syngas stream derived frommethane steam reforming with an epoxide in the presence of acarbonylation catalyst thereby consuming carbon monoxide from the syngasand producing an epoxide carbonylation product,

b) recovering an upgraded gas stream from the first reaction zonewherein the upgraded gas stream has a higher hydrogen to carbon monoxideratio than the starting syngas stream, and

c) in a second reaction zone, utilizing the upgraded gas stream toconduct a second chemical process requiring a hydrogen to carbonmonoxide ratio higher than the ratio in the industrial gas streamutilized in step (a).

FIG. 2 shows a schematic of another embodiment of such a process. Withreference to FIG. 2, a methane steam reforming reactor 102 which is fedwith steam and methane to produce syngas stream 103. Gas stream 103 isfed to carbonylation reactor 200 along with epoxide (via stream 201).The epoxide and carbon monoxide react in the presence of a carbonylationcatalyst in reactor 200 to produce product stream P1 containingcarbonylation products and a hydrogen-enriched gas stream 104. Thehydrogen enriched gas stream 104 can be used for known purposesrequiring hydrogen or hydrogen-rich syngas. For example, as shown inFIG. 2, gas stream 104 can optionally be fed to a chemical reactor whichconsumes hydrogen to make chemical products (e.g. ammonia orhydrogenated products), or to a fuel cell to produce electricitycollectively represented by reactor 500 and outputs P3 and V1. Asdescribed more fully below, in certain embodiments, carbonylationreactor 200 is operated under conditions such that essentially all ofthe carbon monoxide in syngas stream 103 is consumed, in which casestream 104 consists of substantially pure hydrogen. These embodimentshave the attractive feature of eliminating the need for a pressure swingadsorption unit (e.g. PSA 402) or related purification stages.

In another aspect, provided is an integrated process for the productionof hydrogen and commodity chemicals derived from beta lactonecarbonylation. In certain embodiments, such methods comprise:

a) in a first reaction zone, contacting syngas with a beta propiolactonein the presence of a carbonylation catalyst thereby consuming carbonmonoxide from the syngas and producing a succinic anhydride product,

b) recovering an upgraded gas stream from the first reaction zonewherein the upgraded gas stream has a higher hydrogen to carbon monoxideratio than the starting syngas stream, and

c) in a second reaction zone, utilizing the upgraded gas stream toconduct a second chemical process requiring a hydrogen to carbonmonoxide ratio higher than the ratio in the industrial gas streamutilized in step (a).

FIG. 3 shows a schematic of an exemplary process according to thisembodiment. As shown in FIG. 3, Syngas reactor 103 which is fed withappropriate inputs and produces syngas stream 103. Gas stream 103 is fedto carbonylation reactor 200 along with a beta lactone (via stream 202).The lactone and carbon monoxide react in the presence of a carbonylationcatalyst in reactor 202 to produce a succinic anhydride product alongwith gas stream 104 which is enriched in hydrogen relative to stream103. As shown, the succinic anhydride can optionally be fed tohydrogenation reactor 501 along with the hydrogen stream 104 andcontacted under hydrogenation conditions to produce tetrahydrofuran(THF), 1,4 butanediol (BDO), or gamma butyrolactone (GBL).

FIG. 4 shows a schematic of another embodiment where the syngas input isupgraded twice by utilizing two carbonylation stages. As shown in FIG.4, syngas is produced in gasifier 100 in the usual fashion, the outputsyngas stream 101 is directed to first carbonylation reactor 200 whereit is contacted with an epoxide and a carbonylation catalyst to producea beta lactone product and hydrogen enriched synthesis gas stream 103.Both the beta lactone and the gas stream 103 are directed to a 2^(nd)carbonylation reactor 202 where they are further reacted in the presenceof a carbonylation catalyst (which may be the same or different from thecatalyst in the 1^(st) carbonylation reactor) to produce a succinicanhydride product stream P3 along with a hydrogen stream 105. As shownthese streams may optionally be combined in hydrogenation reactor 502where the anhydride reacts with the hydrogen to produce a product streamP4 containing products selected from the group consisting of THF, BDOand GBL.

Having generally described the spirit of the methods encompassed herein,the following sections provide additional details regarding thecompositions of the feedstocks, process streams and products as well asappropriate process conditions and apparatus for practicing theprocesses described herein.

I) Syngas Production

The methods described herein do not place any specific restrictions onthe method by which the syngas input is produced or on the specificcomposition of the syngas. The terms “synthesis gas” or “syngas” as usedherein refer to any gaseous mixture of carbon monoxide and hydrogen.Such mixtures are typically produced from a carbonaceous feedstsock.Syngas production methods include gasification of coal or biomass andsteam reforming of methane or other gaseous or liquid hydrocarbons andsimilar processes.

In certain embodiments, the syngas stream fed to the carbonylationreactor in the methods described herein is characterized in that it hasan H₂ to CO ratio between about 0.4:1 and about 1.5:1. Such a range istypical for syngas from solids gasification which tends to producecarbon rich syngas. In certain embodiments, the syngas stream fed to thecarbonylation reactor is characterized in that it has an H₂ to CO ratioof 0.4:1, about 0.5:1, about 0.6:1, about 0.7:1, about 0.8:1, about 1:1,about 1.2:1, about 1.4:1, or about 1.5:1. In certain embodiments, thesyngas stream fed to the carbonylation reactor is characterized in thatit has an H₂ to CO ratio less than about 1.6:1, less than about 1.5:1,less than about 1.3:1, less than about 1.2:1, less than about 1.1:1,less than about 1:1, less than about 0.8:1, less than about 0.7:1, orless than about 0.6:1.

In certain embodiments, the syngas stream fed to the carbonylationreactor in the methods described herein is characterized in that it hasan H₂ to CO ratio between about 1.5:1 and about 3:1. Such a range istypical for steam reforming processes utilizing methane or other lightaliphatic feedstocks. In certain embodiments, the syngas stream fed tothe carbonylation reactor is characterized in that it has an H₂ to COratio of 1.5:1, about 1.6:1, about 1.8:1, about 2:1, about 2.4:1, about2.8:1, or about 3:1. In certain embodiments, the syngas stream fed tothe carbonylation reactor is characterized in that it has an H₂ to COratio than about 3:1, less than about 2.8:1, less than about 2.5:1, lessthan about 2.2:1, or less than about 2:1.

Syngas typically contains varying amounts of CO₂. In many catalyticprocesses the CO₂ must be removed prior to using the gas. This issue ismore acute in processes relying on biomass gasification since the highoxygen content of biobased feedstocks typically produces syngas withhigh CO₂ content (often 20% or more). The presence of CO₂ not onlypotentially compromises downstream catalytic processes, but its presencein the syngas stream means that any process steps (e.g. compression ordesulfurization) performed prior to removal of the CO₂ are lessefficient since the CO₂ dilutes the stream and therefore requires higherprocessing capacity. Unexpectedly, the applicants have discovered thatepoxide carbonylation reactions promoted by certain classes of catalystsdescribed below are tolerant of high levels of CO₂ in the syngas stream.

Therefore, in certain embodiments, the syngas stream fed to thecarbonylation reactor in the methods described herein is characterizedin that it contains CO₂. In certain embodiments, the syngas streamcontains between about 1 mole percent and about 30 mole percent CO₂. Incertain embodiments, the syngas stream contains between about 1 molepercent and about 5 mole percent CO₂, between about 5 mole percent andabout 10 mole percent CO₂, between about 10 mole percent and about 20mole percent CO₂, or between about 20 mole percent and about 40 molepercent CO₂.

Nevertheless, in some circumstances, it may be desirable to provide asyngas stream which contains little or no CO₂ to the carbonylation step.Therefore, in certain embodiments, the syngas stream fed to thecarbonylation reactor in the methods described herein is characterizedin that it contains little or no CO₂. In certain embodiments, the syngasstream fed to the carbonylation reactor contains less than about 2000ppm, less than about 1000 ppm, less than about 500 ppm, less than about200 ppm, less than about 100 ppm, less than about 50 ppm, less thanabout 25 ppm, or less than about 10 ppm CO₂.

Without being bound by theory or thereby limiting the scope of theclaimed invention, it is believed that the presence of sulfur compoundsin the syngas stream may be deleterious to the epoxide carbonylationreactions described herein. Therefore, in certain embodiments, thesyngas stream fed to the carbonylation reactor is substantially free ofsulfur. In certain embodiments, the syngas stream fed to thecarbonylation reactor contains less than about 500 ppm, less than 200ppm, less than about 100 ppm, less than about 50 ppm, less than about 40ppm, or less than about 25 ppm sulfur. In certain embodiments, thesyngas stream fed to the carbonylation reactor contains less than about10 ppm, less than about 5 ppm, less than about 2 ppm, less than about 1ppm, or less than about 0.5 ppm sulfur. In certain embodiments, thesyngas stream fed to the carbonylation reactor contains less than about0.2 ppm, less than about 0.1 ppm, less than about 0.05 ppm, less thanabout 0.01 ppm, or less than about 0.001 ppm sulfur.

It will be appreciated by the skilled artisan that production of syngasis a mature technology which is capable of operating with a diversearray of feedstocks and that numerous process conditions and catalystsfor production of syngas are known in the art. Likewise apparatus andmethods for the handling and purification of syngas are well known. Assuch, the selection of appropriate feedstocks and process conditions toproduce syngas suitable for practice of the inventive methods describedherein will be apparent to the skilled artisan based on the teachingsand disclosure herein. The exact choice of feedstocks and processingmethods is likely to depend on the local availability of materials andprevailing economic conditions.

II) Carbonylation Reaction Conditions

As described above and in the classes and subclasses herein, the methodsdescribed herein comprise contacting the syngas stream with acarbonylation catalyst in the presence of an epoxide or a beta lactone.Catalysts, conditions and processes for these carbonylation reactionsare well known in the art and can be employed in the methods describedherein.

For embodiments where the syngas is reacted with an epoxide, noparticular constraints are placed on the identity of the epoxide. Anyepoxide or mixture of epoxides may be used, though as a generalprinciple those epoxides lacking other reactive functional groups (forexample protic functional groups) are less desirable since there is anincreased likelihood for side reactions with use of such substrates.Also, given the large scale on which syngas production is typicallypracticed, there is a strong preference to utilize epoxides that areavailable in bulk as commodity chemicals.

In certain embodiments where the methods entail epoxide carbonylationreactions, the epoxide is selected from the group consisting of:ethylene oxide, propylene oxide, butylene oxide, 1-hexene oxide,epichlorohydrin, and esters or ethers of glycidol. In certainembodiments, the epoxide is selected from the group consisting ofethylene oxide and propylene oxide. In certain embodiments the epoxideis ethylene oxide. In certain embodiments the epoxide is propyleneoxide.

The catalytic insertion of CO into epoxides is known to yield severalpossible products the identity of which is influenced by the particularcatalyst utilized and the reaction conditions employed. In certainembodiments, the methods comprise carbonylating an epoxide, and theproduct of the carbonylation is selected from the group consisting of: abeta lactone, a 3-hyroxy propionic acid, a succinic anhydride (viadouble carbonylation) and polyesters comprising the alternatingcopolymer of the epoxide and CO.

In certain embodiments, carbonylation results in the formation of a betalactone by the general reaction:

Examples include:

Suitable catalysts and reaction conditions for effecting this reactionare disclosed in published PCT applications: WO2003/050154,WO2004/089923, WO2012/158573, WO2010/118128, WO2013/063191, andWO2014/008232; in U.S. Pat. No. 5,359,081 and U.S. Pat. No. 5,310,948and in the publication “Synthesis of beta-Lactones” J. AM. CHEM. SOC.,vol. 124, 2002, pages 1174-1175.

In certain embodiments, carbonylation results in the formation of apolyester by the general reaction:

Examples include propylene oxide+CO→poly(3-hydroxybutyrate)

In certain embodiments where methods described herein includecarbonylative polymerization, the methods utilize catalysts and/orprocess conditions disclosed in published PCT applicationsWO2003/074585A1, WO2011/063309, or WO2014004858.

In certain embodiments, epoxide carbonylation results in the formationof a succinic anhydride by insertion of two molecules of CO. Suchprocesses conform to the general reaction scheme:

In certain embodiments, where methods described herein include doublecarbonylation of epoxides, the methods utilize catalysts and/or processconditions disclosed in published PCT applications WO2012/030619 andWO2013/122905, and U.S. Pat. No. 8,481,756.

As described above, certain embodiments of the methods described hereincomprise contacting a syngas stream with a beta lactone in the presenceof a carbonylation catalyst to yield a succinic anhydride derivativealong with a hydrogen-enriched syngas stream. Such processes conform tothe general reaction scheme:

The catalysts and/or process conditions disclosed in published PCTapplications WO2012/030619 and WO2013/122905, and U.S. Pat. No.8,481,756, can be utilized to perform such steps.

In certain embodiments, carbonylation catalysts utilized in the presentmethods comprise metal carbonyl complexes. In certain embodiments, thecatalysts comprise metal carbonyl complexes in combination with one ormore other components such as amines, nitrogen-containing heterocycles,Lewis acids, or metal complexes.

In some embodiments, the carbonylation catalyst includes a metalcarbonyl compound. Typically, in one variation, a single metal carbonylcompound is provided, but in certain embodiments mixtures of two or moremetal carbonyl compounds are provided. (Thus, when a provided metalcarbonyl compound “comprises”, e.g., a neutral metal carbonyl compound,it is understood that the provided metal carbonyl compound can be asingle neutral metal carbonyl compound, or a neutral metal carbonylcompound in combination with one or more additional metal carbonylcompounds.) Preferably, the provided metal carbonyl compound is capableof ring-opening an epoxide and facilitating the insertion of CO into theresulting metal carbon bond. Metal carbonyl compounds with thisreactivity are well known in the art and are used for laboratoryexperimentation as well as in industrial processes such ashydroformylation. Additional description of suitable metal carbonylcompounds is provided herein.

As mentioned above, carbonylation catalysts useful for practicingmethods described herein may include one or more additional componentsin combination with a metal carbonyl compound. In certain embodiments,such additional components comprise organic bases such as optionallysubstituted amines, guanidines, and amidines. In certain embodiments,such additional components comprise heterocycles such as optionallysubstituted pyridines, pyrimidines, imidazoles, and the like. In certainembodiments, such additional components comprise neutral Lewis acidssuch as boranes, aluminum alkyls, TiCl₄, BF₃, and the like. In certainembodiments, such additional components comprise cationic Lewis acids.Additional description of suitable cationic Lewis acids is providedherein.

In certain embodiments, the carbonylation catalysts employed in methodsdescribed herein comprise heterogeneous carbonylation catalysts. Incertain embodiments, such heterogeneous catalysts comprise supportedmetal carbonyl compounds. In certain embodiments, carbonylationcatalysts and processes disclosed in WO 2013/063191 may be adapted foruse in methods described herein.

The methods described herein provide no specific limitations on thereaction conditions utilized in the carbonylation step. For practicalapplication on industrial scale, the carbonylation reaction willtypically be performed in a continuous or semi-continuous format. Wherethe carbonylation reaction is performed in a continuous fashion, it maybe conducted in any suitable reactor format, such as plug flow reactors(PFRs), continuous stirred-tank reactors (CSTRs) or any hybrid orcombination of these. Though the carbonylation stage of the methodsherein is often described as a single step, it may in fact occur inmultiple steps such as within a series of continuous stirred tankreactors or a plug flow reactor fed by one or more CSTRs. Continuousoperation requires additional processing steps and suitable apparatus tocontinuously feed reactants, catalysts, solvents and the like as well asprovision to continuously withdraw carbonylation products, recycle thecatalyst and solvents, purge impurities, and the like. A detaileddescription of such processes and apparatus is outside the scope of thisdisclosure since the requisite knowledge is readily available to theskilled artisan. In certain embodiments, the continuous carbonylationprocesses described in published PCT applications WO 2010/118128 WO2012/030619 WO 2013/063191 WO 2013/122905 and WO 2014008232 are suitablefor practicing certain embodiments of the methods described herein.

The syngas will typically be fed to the carbonylation reactor at asuperatmospheric pressure. No particular limits are placed on thepressure utilized. As with similar processes the chosen operatingpressure will require balance of the reaction rate and selectivity at agiven pressure with the cost of the equipment required to operate atthat pressure. In certain embodiments, the syngas is provided to thecarbonylation reactor at a pressure from about 50 psi to about 5,000psi. If the source of the synthesis gas provides a gas stream at apressure lower than the desired pressure in the carbonylation step, thenthe methods will include an additional step of pressurizing the syngasstream prior to contacting it with the epoxide or beta lactone. Incertain embodiments, the carbonylation reactor is integrated with asyngas production source that outputs a pressurized source of syngas andthe carbonylation reactor is run at a pressure substantially the same asthe output from the syngas source.

In certain embodiments, the syngas is provided to the carbonylationreactor at a pressure sufficient to afford a carbon monoxide partialpressure within the reactor from about 0.5 atmospheres to about 350atmospheres. In certain embodiments, the carbon monoxide partialpressure ranges from about 5 to about 100 atmospheres. In certainembodiments, the carbon monoxide partial pressure ranges from about 10to about 50 atmospheres, from about 5 to about 20 atmospheres, fromabout 1 to about 10 atmospheres, or from about 25 to about 50atmospheres. In some embodiments, carbon monoxide partial pressurewithin the carbonylation reactor ranges from about 0.5 atmospheres toabout 10 atmospheres. In some embodiments, a carbon monoxide partialpressure within the carbonylation reactor ranges from about 0.5 to about50, from about 1 to about 10, from about 1 to about 50, from about 1 toabout 100, from about 10 to about 50, from about 10 to about 100, fromabout 50 to about 100, from about 50 to about 200, from about 100 toabout 200, from about 100 to about 250, from about 200 to about 300, orfrom about 200 to about 500 atmospheres. In some embodiments, a carbonmonoxide partial pressure within the carbonylation reactor is about 10atmospheres. In some embodiments, a carbon monoxide partial pressurewithin the carbonylation reactor is about 10, about 20, about 30, about40, about 50, about 100, about 150, or about 200 atmospheres.

In certain embodiment, the step of contacting the syngas stream withepoxide or beta lactone in the presence of a carbonylation catalyst isperformed under conditions such that the hydrogen-to-carbon monoxideratio in the upgraded syngas stream exiting the reactor is maintainedwithin a specific range. In certain embodiments, the desired range isdependent on the identity of the downstream process in which theupgraded gas stream is to be used. For integrated carbonylation-FischerTropsch processes, it is desirable to maintain the H₂ to CO ratio of theupgraded syngas stream around 2:1. For integratedcarbonylation-hydrogenation processes, it is desirable to maintain theH₂ to CO ratio at a high level, or even to consume substantially all ofthe CO in the syngas feed stream such that the upgraded stream containslittle or no CO. Therefore, in certain embodiments, the methodsdescribed herein are characterized in that the upgraded syngas streamobtained from the carbonylation reactor has an H₂ to CO ratio aboveabout 2:1. In certain embodiments, the upgraded syngas stream obtainedfrom the carbonylation reactor has an H₂ to CO ratio above about 2.1:1,above about 2.2:1, above about 2.3:1, above about 2.4:1, above about2.1:1, above about 2.1:1, above about 2.1:1, above about 2.1:1, aboveabout 2.5:1, above about 2.8:1, above about 3:1, above about 3.5:1,above about 4:1, above about 5:1, or above about 10:1. In certainembodiments, the upgraded syngas stream obtained from the carbonylationreactor has an H₂ to CO ratio above about 2.1:1, above about 10:1, aboveabout 20:1, above about 50:1, above about 100:1, above about 200:1,above about 500:1, or above about 1000:1.

In certain embodiments, the methods described herein are characterizedin that the upgraded syngas stream obtained from the carbonylationreactor has an H₂ to CO ratio of about 2:1. In certain embodiments, theupgraded syngas stream obtained from the carbonylation reactor has an H₂to CO ratio of about 2.1:1, about 2.2:1, about 2.5:1, about 3:1, about4:1, about 5:1, or about 10:1.

In certain embodiments, the methods described herein are characterizedin that the upgraded syngas stream obtained from the carbonylationreactor is essentially free of CO. In certain embodiments, the upgradedsyngas stream obtained from the carbonylation reactor contains less than2%, less than 1%, less than 0.5%, less than 0.2%, or less than 0.1% CO.In certain embodiments, the upgraded syngas stream obtained from thecarbonylation reactor contains less than 500 ppm, less than 400 ppm,less than 200 ppm, less than 100 ppm, less than 50 ppm, less than 25ppm, less than 10 ppm, less than 5 ppm, or less than 1 ppm CO.

III) Utilization of the Upgraded Syngas Stream

The upgraded syngas stream from the carbonylation reactor may berecovered and handled by any suitable means. Typically the upgradedsyngas stream will exit the carbonylation reactor via a gas vent, aback-pressure regulator or an outlet port which may include provisionfor liquids separation, recompression, scrubbing, drying, chilling orheating, and the like as is typically performed in industry. In certainembodiments, the carbonylation reactor is operated at a higher pressurethan the downstream process fed with the upgraded syngas stream thatexits the carbonylation reactor. This has the advantage of not requiringrecompression of the upgraded syngas stream. Nonetheless, this is notalways possible if the downstream process is one that requires highhydrogen partial pressures. In this case, the methods described hereinwill include compressing the upgraded syngas stream prior to utilizingit in next process.

In certain embodiments, the upgraded syngas stream exiting thecarbonylation reactor will contain impurities that must be removed priorto utilization of the upgraded stream. For example, if the streamcontains carbon dioxide and the downstream process is not tolerant ofCO₂, then the methods necessarily require an intermediate step to scrubCO₂ from the upgraded stream. Such methods are well known in the art andmay include membrane separation, pressure swing adsorption, chemicaladsorption, cryotreatment and the like. In certain embodiments, volatileresidues from the carbonylation reactor may be present in the upgradedsyngas stream. Such residues may include solvent, unreacted epoxide,carbonylation side products such as acetaldehyde, volatile metalcarbonyl residues and the like. In certain embodiments, the upgradedsyngas stream is treated to remove such impurities prior to utilizationof the stream in a downstream process. In certain embodiments where thedownstream process is tolerant of such residues, it may be preferable toleave the impurities in the upgraded syngas stream and purge them at alater stage in the process.

As described above a feature of some methods described herein is the useof the upgraded syngas stream in a downstream process. Preferably, thecarbonylation stage of the methods increases the H₂:CO ratio in thestream to a range that is desirable for the downstream process.

In certain embodiments, the downstream process comprises Fischer-Tropsch(FT) synthesis. FT technology is a mature field and appropriateoperating conditions, apparatus, catalysts and product isolationtechniques for FT processes are well known in the art. The skilledartisan utilizing the wealth of knowledge available in the FT field,together with the teachings herein, will readily apprehend suitableconfigurations for the FT step described in methods herein. An overviewof FT technology is provided in Advance Catalysis, Volume 186, pp 3-12.

In certain embodiments the downstream process in which the upgradedsyngas stream is utilized is an FT gas-to-liquid process for theproduction of fuels and/or chemicals such as olefins and/or alcohols. Incertain embodiments, the downstream process in which the upgraded syngasstream is utilized is a Low Temperature FT synthesis (LTFT). In certainembodiments, the downstream process in which the upgraded syngas streamis utilized is a High Temperature FT synthesis (HTFT). The FischerTropsch reactor in which the upgraded syngas stream is utilized may beof any known configuration. Suitable configurations include multitubularfixed bed reactors, entrained flow reactors, slurry reactors, bubblereactors, fluidized bed reactors, and riser reactors. Likewise, anyknown FT catalyst system may be employed in the present methods.Suitable catalysts include, for example, cobalt, iron, ruthenium,nickel, and any combination of two or more of these. The FT catalystsmay include additional components as are known in the art includingalkali metals, copper, manganese, lanthanide metals or compounds,actinide metals or compounds, alumina, zirconia, and the like.

In certain embodiments, the downstream process in which the upgradedsyngas stream is utilized is a process for the production of methane.Suitable catalysts and conditions for methane synthesis from syngas areknown in the art and the skilled artisan utilizing the teachings hereinwith the known art will apprehend suitable conditions, apparatus andcatalyst systems to effect the conversion of the upgraded syngas streamto methane.

In certain embodiments, the downstream process in which the upgradedsyngas stream is utilized is a process for the production of methanol.Suitable catalysts and conditions for methanol synthesis from syngas areknown in the art and the skilled artisan utilizing the teachings hereinwith the known art will apprehend suitable conditions, apparatus andcatalyst systems to effect the conversion of the upgraded syngas streamto methanol.

In certain embodiments the downstream process in which the upgradedsyngas stream is utilized is a process for the production of dimethylether. Suitable catalysts and conditions for methanol synthesis fromsyngas are known in the art and the skilled artisan utilizing theteachings herein with the known art will apprehend suitable conditions,apparatus and catalyst systems to effect the conversion of the upgradedsyngas stream to methanol.

In other embodiments, the integrated upgraded syngas stream is utilizedas a fuel. For example, the upgraded syngas stream can be fed to a fuelcell, combusted in a turbine or boiler, or used to fuel an internalcombustion engine. Therefore, depending on the process utilized,processes herein may provide an output comprising steam, thermal energy,electrical energy, or mechanical energy. Due to the higher H₂ to COratio in the upgraded gas stream, the upgraded stream may have a higherenergy content than the starting syngas stream (it will be appreciatedthat whether or not this is the case will depend on the amount of othergasses such as CO₂ that may also be present in the streams).

IV) Integrated Production of FT Products and EO Carbonylation Products

As described above, in certain embodiments, provided are methods for theintegrated production of chemicals from syngas derived fromgasification.

In certain embodiments, such processes produce as final outputs, betapropiolactone or polypropiolactone (or derivatives of these such asacrylic acid, acrylate esters or superabsorbent polymers) by ethyleneoxide carbonylation and FT products such as liquid fuels and relatedchemicals.

In certain embodiments, methods described herein comprise:

a) gasifying a carbonaceous solid to provide a syngas stream having anH₂ to CO ratio in the range from about 0.4:1 to about 1.2:1;

b) feeding this syngas stream to an epoxide carbonylation reactor wherethe syngas stream is contacted with ethylene oxide in the presence of acarbonylation catalyst to deplete the syngas of at least a portion ofits CO content and provide a carbonylation product selected from thegroup consisting of: beta propiolactone, and polypropiolactone;

c) recovering an upgraded syngas stream from the carbonylation reactorcharacterized in that the upgraded stream has a higher H₂ to CO ratiothan the syngas stream provided by step (a); and

d) feeding the upgraded syngas stream to a Fischer Tropsch reactor toproduce a product selected from the group consisting of: liquid fuels,oils, waxes, olefins, alcohols, and any combination of two or more ofthese.

In certain embodiments, step (a) of the method above comprises coalgasification. In certain embodiments, such methods are characterized inthat the syngas stream in step (a) has an H₂ to CO ratio of from about0.6:1 to about 0.8:1. In certain embodiments, such methods arecharacterized in that the syngas stream in step (a) has an H₂ to COratio of about 0.7:1.

In certain embodiments, step (a) of the method above comprises biomassgasification. In certain embodiments, the biomass is selected from thegroup consisting of: corn stover, sugar cane bagasse, switch grass,municipal solid waste, and wood waste. In certain embodiments, suchmethods are characterized in that the syngas stream in step (a) has anH2 to CO ratio of from about 0.4:1 to about 0.8:1. In certainembodiments, such methods are characterized in that the syngas stream instep (a) has an H₂ to CO ratio of about 0.6:1. In certain embodiments,such methods are characterized in that the syngas stream in step (a) hasan H₂ to CO ratio of about 0.5:1.

In certain embodiments, the method above further comprises compressingthe syngas stream prior to feeding it to the carbonylation reactor. Incertain embodiments, the method above further comprises removingsulfurous compounds from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above furthercomprises drying the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above furthercomprises removing CO₂ from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above ischaracterized in that CO₂ is not removed from the syngas stream prior tofeeding it to the carbonylation reactor.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method further comprises convertingthe beta propiolactone to acrylic acid, or acrylate esters.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method further comprises convertingthe beta propiolactone to succinic anhydride. In certain embodimentssuch methods comprise an additional step of converting the succinicanhydride to a product selected from the group consisting of: succinicacid, 1,4 butanediol, tetrahydrofuran, gamma butyrolactone, or anycombination of two or more of these.

In certain embodiments where the method above further comprisesconverting beta propiolactone to succinic anhydride, the conversion isconducted in a second carbonylation reactor. In certain embodiments, thesecond carbonylation reactor is also fed with the syngas stream producedin step (a) where it is contacted with the beta propiolactone in thepresence of a carbonylation catalyst to deplete the syngas of at least aportion of its CO content and provide succinic anhydride as a secondcarbonylation product. In certain embodiments, a second upgraded syngasstream, characterized in that it has a higher H₂ to CO ratio that thesyngas stream produced in step (a) is recovered from the secondcarbonylation reactor. In certain embodiments, the first and secondupgraded syngas streams are combined and utilized in step (d).

In certain embodiments where the method above further comprisesconverting beta propiolactone to succinic anhydride, the conversion isconducted in a second carbonylation reactor which is fed with theupgraded syngas stream produced in step (b) where it is contacted withthe beta propiolactone in the presence of a carbonylation catalyst tofurther deplete the upgraded syngas stream of its CO thereby providing atwice-upgraded syngas stream having a higher H₂ to CO ratio than theupgraded syngas stream from step (c). In certain embodiments, the methodcomprises an additional step of recovering the twice upgraded syngasstream from the second carbonylation reactor and feeding it to the FTreactor in step (d).

In certain embodiments, the product of step (b) of the method abovecomprises polypropiolactone and the method further comprises pyrolyzingthe polypropiolactone to produce acrylic acid.

In certain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound. In certainembodiments, the metal carbonyl compound is selected from any of thosedescribed herein. In certain embodiments, the metal carbonyl compoundcomprises a cobalt carbonyl compound. In certain embodiments, metalcarbonyl compound comprises a rhodium carbonyl compound. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises a metal carbonyl compound in combination with anothercomponent selected from the group consisting of: organic bases, neutralLewis acids, and cationic Lewis acids. In certain embodiments, thecarbonylation catalyst in step (b) of the method above comprises ananionic cobalt carbonyl compound in combination with a cationic Lewisacid. In certain embodiments, such cationic Lewis acids comprise metalligand complexes. In certain embodiments, the metal ligand complexescomprise any complex described herein. In certain embodiments, suchmetal ligand complexes comprise a metal atom coordinated to amultidentate ligand. In certain embodiments, such metal ligand complexescomprise an aluminum or chromium atom. In certain embodiments, suchmetal ligand complexes comprise a porphyrin or salen ligand. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises any combination of a metal carbonyl compound and a metalcomplex, as described herein.

In certain embodiments, step (c) in the method above is characterized inthat the upgraded syngas stream recovered has an H₂ to CO ratio betweenabout 1.2:1 and about 3:1. In certain embodiments, the upgraded syngasstream recovered has an H₂ to CO ratio between about 1.6:1 and about2.8:1, between about 1.8:1 and about 2.6:1, between about 1.8:1 andabout 2.2:1, or between about 1.9:1 and about 2.1:1. In certainembodiments, the upgraded syngas stream recovered has an H₂ to CO ratioof about 2:1.

In certain embodiments, the method above is characterized in that thereaction pressure in the carbonylation reactor is higher than thereaction pressure in the FT reactor. In certain embodiments, theupgraded syngas stream is fed to the FT reactor without an intermediatecompression step. In certain embodiments, the upgraded syngas streamexits the carbonylation reactor via a backpressure regulator and is feddirectly to the FT reactor.

In certain embodiments, the method above is characterized in that theupgraded syngas stream is treated to remove one or more components priorto feeding the stream to the FT reactor. In certain embodiments, theupgraded syngas stream is treated to remove residual solvent prior tofeeding the stream to the FT reactor. In certain embodiments, theupgraded syngas stream is treated to remove residual epoxide prior tofeeding the stream to the FT reactor. In certain embodiments, theupgraded syngas stream is treated to remove carbon dioxide prior tofeeding the stream to the FT reactor.

In certain embodiments, the method above is characterized in that the FTreactor in step (d) is a Low Temperature FT synthesis (LTFT) reactor. Incertain embodiments, the downstream process in which the upgraded syngasstream is utilized is a High Temperature FT synthesis (HTFT) reactor.

In certain embodiments, the method above is characterized in that theoverall process has a carbon efficiency greater than 50%. That is, atleast 50% of the carbon atoms fed to the gasification reactor arecontained in the combined products from the EO carbonylation reactor andthe FT reactor. In certain embodiments, the method is characterized inthat the overall process has a carbon efficiency greater than 55%,greater than 60%, greater than 62%, greater than 63%, greater than 64%,or greater than 65%. In certain embodiments, the method is characterizedin that the overall process has a carbon efficiency greater than 66%,greater than 67%, greater than 68%, greater than 69%, or greater than70%. In certain embodiments, the method is characterized in that theoverall process has a carbon efficiency between about 50% and about 60%.In certain embodiments, the method is characterized in that the overallprocess has a carbon efficiency between about 55% and about 60%. Incertain embodiments, the method is characterized in that the overallprocess has a carbon efficiency between about 60% and about 64%. Incertain embodiments, the method is characterized in that the overallprocess has a carbon efficiency between about 64% and about 67%. Incertain embodiments, the method is characterized in that the overallprocess has a carbon efficiency between about 67% and about 70%.

In certain embodiments, the method above is characterized in that the FTprocess in step (d) is fed with syngas from the gasification process instep (a) without utilizing the water gas shift reaction to increase itsH₂ to CO ratio.

V) Integrated Production of Hydrogen and EO Carbonylation Products

As described above, in certain embodiments, provided are methods for theintegrated production of chemicals and hydrogen.

In certain embodiments, such processes produce as final outputs, betapropiolactone or polypropiolactone (or derivatives of these such asacrylic acid, acrylate esters or superabsorbent polymers) by ethyleneoxide carbonylation and hydrogen or products of hydrogen such aselectrical energy, ammonia, or hydrogenated chemicals.

In certain embodiments, the methods comprise:

a) producing a syngas stream by steam reforming of methane or otherlower aliphatic compounds;

b) feeding this syngas stream to an epoxide carbonylation reactor wherethe syngas stream is contacted with ethylene oxide in the presence of acarbonylation catalyst to deplete the syngas of at least a portion ofits CO content and provide a carbonylation product selected from thegroup consisting of: beta propiolactone, and polypropiolactone; and

c) recovering a hydrogen stream from the carbonylation reactorcharacterized in that the hydrogen stream has a higher H₂ to CO ratiothan the syngas stream provided by step (a).

In certain embodiments, step (a) of the method above comprises steammethane reforming. In certain embodiments, such methods arecharacterized in that the syngas stream in step (a) has an H₂ to COratio of from about 2.8:1 to about 3.2:1. In certain embodiments, suchmethods are characterized in that the syngas stream in step (a) has anH₂ to CO ratio of about 3:1.

In certain embodiments, the method above further comprises compressingthe syngas stream prior to feeding it to the carbonylation reactor. Incertain embodiments, the method above further comprises removingsulfurous compounds from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above furthercomprises drying the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above furthercomprises removing CO₂ from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above ischaracterized in that CO₂ is not removed from the syngas stream prior tofeeding it to the carbonylation reactor.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method comprises an additional stepof converting the beta propiolactone to acrylic acid, or acrylateesters.

In certain embodiments, the product of step (b) of the method abovecomprises polypropiolactone and the method further comprises pyrolyzingthe polypropiolactone to produce acrylic acid.

In certain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound. In certainembodiments, the metal carbonyl compound is selected from any of thosedescribed herein. In certain embodiments, the metal carbonyl compoundcomprises a cobalt carbonyl compound. In certain embodiments, metalcarbonyl compound comprises a rhodium carbonyl compound. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises a metal carbonyl compound in combination with anothercomponent selected from the group consisting of: organic bases, neutralLewis acids, and cationic Lewis acids. In certain embodiments, thecarbonylation catalyst in step (b) of the method above comprises ananionic cobalt carbonyl compound in combination with a cationic Lewisacid. In certain embodiments, such cationic Lewis acids comprise metalligand complexes. In certain embodiments, the metal ligand complexescomprise any complex described herein. In certain embodiments, suchmetal ligand complexes comprise a metal atom coordinated to amultidentate ligand. In certain embodiments, such metal ligand complexescomprise an aluminum or chromium atom. In certain embodiments, suchmetal ligand complexes comprise a porphyrin or salen ligand. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises any combination of a metal carbonyl compound and a metalcomplex, as described herein.

In certain embodiments, the method above is characterized in that thehydrogen stream recovered in step (c) has an H₂ to CO ratio betweenabout 4:1 and about 1,000:1. In certain embodiments, the upgraded syngasstream recovered has an H₂ to CO ratio between about 5:1 and about 10:1,between about 10:1 and about 50:1, between about 50:1 and about 100:1,or between about 100:1 and about 1000:1. In certain embodiments, thehydrogen stream contains essentially no CO.

In certain embodiments, the method above is characterized in that thehydrogen stream is treated to remove one or more components prior touse. In certain embodiments, the hydrogen stream is treated to removeresidual solvent prior to use. In certain embodiments, the hydrogenstream is treated to remove residual epoxide prior to use. In certainembodiments, the hydrogen stream is treated to remove carbon dioxideprior to use.

In certain embodiments, the method above is characterized in that thehydrogen stream is utilized on site for a process selected from: ammoniasynthesis, powering a fuel cell, hydrogenation, and any combination oftwo or more of these. In certain embodiments, the hydrogen is compressedand distributed for use elsewhere.

In certain embodiments, the method above is characterized in that theoverall process has a carbon efficiency greater than 50%. That is, atleast 50% of the carbon atoms fed to the steam reforming reactor arecontained in products from the EO carbonylation reactor. In certainembodiments, the method is characterized in that the overall process hasa carbon efficiency greater than 55%, greater than 60%, greater than62%, greater than 63%, greater than 64%, or greater than 65%. In certainembodiments, the method is characterized in that the overall process hasa carbon efficiency greater than 66%, greater than 67%, greater than68%, greater than 69%, or greater than 70%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 50% and about 60%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 55% and about 60%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 60% and about 64%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 64% and about 67%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 67% and about 70%.

VI) Integrated Production of Hydrogen and C4 Chemical Products

In certain embodiments, provided are methods for the integratedproduction of C4 chemicals and hydrogen.

In certain embodiments, such processes produce as final outputs,succinic anhydride (or derivatives of succinic anhydride such assuccinic acid, 1,4-butanediol, THF and gamma butyrolactone) and hydrogenor products of hydrogen such as electrical energy, ammonia, orhydrogenated chemicals.

In certain embodiments, the methods comprise:

a) producing a syngas stream by steam reforming of methane or otherlower aliphatic compounds;

b) feeding this syngas stream to a carbonylation reactor where thesyngas stream is contacted with a substrate selected from ethyleneoxide, beta propiolactone and combinations of these, in the presence ofa carbonylation catalyst to deplete the syngas of at least a portion ofits CO content and provide succinic anhydride as a carbonylationproduct; and

c) recovering a hydrogen stream from the carbonylation reactorcharacterized in that the hydrogen stream has a higher H₂ to CO ratiothan the syngas stream provided by step (a).

In certain embodiments, step (a) of the method above comprises steammethane reforming. In certain embodiments, such methods arecharacterized in that the syngas stream in step (a) has an H₂ to COratio of from about 2.8:1 to about 3.2:1. In certain embodiments, suchmethods are characterized in that the syngas stream in step (a) has anH₂ to CO ratio of about 3:1.

In certain embodiments, the method above further comprises compressingthe syngas stream prior to feeding it to the carbonylation reactor. Incertain embodiments, the method above further comprises removingsulfurous compounds from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above furthercomprises drying the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above furthercomprises removing CO₂ from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above ischaracterized in that CO₂ is not removed from the syngas stream prior tofeeding it to the carbonylation reactor.

In certain embodiments, step (b) of the method above comprises doublecarbonylation of ethylene oxide to produce the succinic anhydride. Incertain embodiments, the double carbonylation proceeds in the presenceof a single carbonylation catalyst, while in other embodiments, thedouble carbonylation proceeds with the aid of two or more separatecatalysts.

In certain embodiments, the double carbonylation of ethylene oxideoccurs in a single reactor, while in other embodiments, the twocarbonylation steps occur in the two or more reactors. The utilizationof two reactors is advantageous in certain embodiments, because of thekinetics of the two carbonylation steps. Without being bound by theoryor thereby limiting the scope of the present invention, it is believedthat carbonylation of ethylene oxide to produce beta lactones may bezero order in epoxide concentration (e.g., the rate of EO conversion isindependent of EO concentration. Therefore, it is believed that acontinuous EO carbonylation reactor can be operated efficiently understeady state conditions and maintain a low concentration of EO in theproduct stream. Conversely, it is believed that the carbonylation ofbeta lactones is not zero order in lactone and the reaction rate issensitive to lactone concentration. Therefore, to achieve highconversion in carbonylation of lactones it is believed this step is bestperformed under plug flow conditions so that a significant proportion ofthe lactone is consumed. Therefore, in certain embodiments of the methoddescribed above, the conversion of ethylene oxide to succinic anhydrideoccurs in two or more reactors. In certain embodiments, the reactors areoperated under different conditions to maximize the efficiency of eachof the two carbonylation steps. In certain embodiments ethylene oxide iscontacted with the syngas stream in a first carbonylation reactor toprovide beta propiolactone as an intermediate product which is fed to asecond carbonylation reactor where it is converted to succinicanhydride. In certain embodiments of such methods, the firstcarbonylation reactor is a steady state reactor. In certain embodiments,the second reactor is a plug flow reactor. In certain embodiments ofsuch methods, the first carbonylation reactor is a steady state reactorand the second reactor is a plug flow reactor. In certain embodiments,the second carbonylation reactor is fed with an upgraded syngas streamrecovered from the first carbonylation reactor where the upgraded syngasstream has a higher H₂ to CO ratio than the syngas stream produced instep (a).

In other embodiments where the carbonylation occurs in two or morereactors, each of two carbonylation reactors is fed with the syngasstream from step (a). In certain embodiments, a hydrogen stream isobtained from each of the carbonylation reactors. In certain embodimentswhere multiple hydrogen streams are obtained from two or more reactors,they are combined. In other embodiments, each of the streams is usedseparately.

In certain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound. In certainembodiments, the metal carbonyl compound is selected from any of thosedescribed herein. In certain embodiments, the metal carbonyl compoundcomprises a cobalt carbonyl compound. In certain embodiments, metalcarbonyl compound comprises a rhodium carbonyl compound. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises a metal carbonyl compound in combination with anothercomponent selected from the group consisting of: organic bases, neutralLewis acids, and cationic Lewis acids. In certain embodiments, thecarbonylation catalyst in step (b) of the method above comprises ananionic cobalt carbonyl compound in combination with a cationic Lewisacid. In certain embodiments, such cationic Lewis acids comprise metalligand complexes. In certain embodiments, the metal ligand complexescomprise any complex described herein. In certain embodiments, suchmetal ligand complexes comprise a metal atom coordinated to amultidentate ligand. In certain embodiments, such metal ligand complexescomprise an aluminum or chromium atom. In certain embodiments, suchmetal ligand complexes comprise a porphyrin or salen ligand. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises any combination of a metal carbonyl compound and a metalcomplexes described herein.

In certain embodiments, the method above is characterized in that thehydrogen stream recovered in step (c) has an H₂ to CO ratio betweenabout 4:1 and about 1,000:1. In certain embodiments, the upgraded syngasstream recovered has an H₂ to CO ratio between about 5:1 and about 10:1,between about 10:1 and about 50:1, between about 50:1 and about 100:1,or between about 100:1 and about 1000:1. In certain embodiments, thehydrogen stream contains essentially no CO.

In certain embodiments, the method above is characterized in that thehydrogen stream is treated to remove one or more components prior touse. In certain embodiments, the hydrogen stream is treated to removeresidual solvent prior to use. In certain embodiments, the hydrogenstream is treated to remove residual epoxide prior to use. In certainembodiments, the hydrogen stream is treated to remove carbon dioxideprior to use.

In certain embodiments, the method above is characterized in that thehydrogen stream is utilized on site for a process selected from: ammoniasynthesis, powering a fuel cell, hydrogenation, and any combination oftwo or more of these. In certain embodiments, the hydrogen is compressedand distributed for use elsewhere.

In certain embodiments, the hydrogen stream is utilized forhydrogenation of the succinic anhydride produced in step (b). In certainembodiments, the hydrogenation of succinic anhydride from step (b) withthe hydrogen stream from step (c) produces 1,4-butanediol. In certainembodiments, the hydrogenation of succinic anhydride from step (b) withthe hydrogen stream from step (c) produces THF. In certain embodiments,the hydrogenation of succinic anhydride from step (b) with the hydrogenstream from step (c) produces gamma butyrolactone. Methods and catalystsfor conversion of maleic and succinic anhydride or their correspondingacids to the products 1,4-BDO, THF and GBL are known in the art and canbe adapted by the skilled artisan to serve in the present methods.

In certain embodiments, the method above is characterized in that theoverall process has a carbon efficiency greater than 50%. That is, atleast 50% of the carbon atoms fed to the steam reforming reactor arecontained in products from the EO carbonylation reactor. In certainembodiments, the method is characterized in that the overall process hasa carbon efficiency greater than 55%, greater than 60%, greater than62%, greater than 63%, greater than 64%, or greater than 65%. In certainembodiments, the method is characterized in that the overall process hasa carbon efficiency greater than 66%, greater than 67%, greater than68%, greater than 69%, or greater than 70%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 50% and about 60%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 55% and about 60%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 60% and about 64%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 64% and about 67%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency between about 67% and about 70%.

In certain embodiments, step (b) of the method above comprises twosubsteps. In a first substep, the syngas stream from step (a) iscontacted with ethylene oxide to provide beta propiolactone along withan upgraded syngas stream having a higher H₂ to CO ratio than the syngasstream from step (a) and, in a second substep, the beta propiolactone isdirected to a second carbonylation reactor where it is contacted withthe upgraded syngas stream in the presence of a carbonylation catalyst(which may be the same as or different from the carbonylation catalystutilized in the first substep) to convert the beta propiolactone tosuccinic anhydride. In certain embodiments such methods further compriseconverting the succinic anhydride to a product selected from the groupconsisting of: succinic acid, 1,4 butanediol, tetrahydrofuran, gammabutyrolactone, or any combination of two or more of these.

In certain embodiments where the method above further comprisesconverting beta propiolactone to succinic anhydride, the conversion isconducted in a second carbonylation reactor. In certain embodiments, thesecond carbonylation reactor is fed with the upgraded syngas streamproduced in step (b) where the upgraded syngas is contacted with thebeta propiolactone in the presence of a carbonylation catalyst tofurther deplete the upgraded syngas stream of its CO thereby providing atwice-upgraded syngas stream having a higher H₂ to CO ratio than theupgraded syngas stream from step (c).

VII) Integrated Production of Methanol and EO Carbonylation Products

As described above, in certain embodiments, provided are methods for theintegrated production of methanol from syngas derived from gasification.

In certain embodiments, such processes produce as final outputs, betapropiolactone or polypropiolactone (or derivatives of these such asacrylic acid, acrylate esters or superabsorbent polymers) by ethyleneoxide carbonylation and methanol or methanol-derived products suchdimethyl ether or olefins via a methanol-to-olefins process (MTO).

In certain embodiments, the methods comprise:

a) treating a carbon-based feedstock to provide a syngas stream having aH₂ to CO ratio less than 2:1;

b) feeding this syngas stream to an epoxide carbonylation reactor wherethe syngas stream is contacted with ethylene oxide in the presence of acarbonylation catalyst to deplete the syngas of at least a portion ofits CO content and provide a carbonylation product selected from thegroup consisting of: beta propiolactone, polypropiolactone and succinicanhydride;

c) recovering an upgraded syngas stream from the carbonylation reactorcharacterized in that the upgraded stream has a higher H₂ to CO ratiothan the syngas stream provided by step (a); and

d) feeding the upgraded syngas stream to a methanol synthesis reactor.

In certain embodiments, step (a) of the method above comprises coalgasification. In certain embodiments, such methods are characterized inthat the syngas stream in step (a) has an H₂ to CO ratio of from about0.6:1 to about 0.8:1. In certain embodiments, such methods arecharacterized in that the syngas stream in step (a) has an H₂ to COratio of about 0.7:1.

In certain embodiments, step (a) of the method above comprises biomassgasification. In certain embodiments, the biomass is selected from thegroup consisting of: corn stover, sugar cane bagasse, switch grass,municipal solid waste, and wood waste. In certain embodiments, suchmethods are characterized in that the syngas stream in step (a) has anH₂ to CO ratio of from about 0.4:1 to about 0.8:1. In certainembodiments, such methods are characterized in that the syngas stream instep (a) has an H₂ to CO ratio of about 0.6:1. In certain embodiments,such methods are characterized in that the syngas stream in step (a) hasan H₂ to CO ratio of about 0.5:1.

In certain embodiments, the method above further comprises compressingthe syngas stream prior to feeding it to the carbonylation reactor. Incertain embodiments, the method above further comprises removingsulfurous compounds from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above furthercomprises drying the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above furthercomprises removing CO₂ from the syngas stream prior to feeding it to thecarbonylation reactor. In certain embodiments, the method above ischaracterized in that CO₂ is not removed from the syngas stream prior tofeeding it to the carbonylation reactor.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method further comprises convertingthe beta propiolactone to acrylic acid, or acrylate esters.

In certain embodiments, the product of step (b) of the method abovecomprises beta propiolactone and the method further comprises convertingthe beta propiolactone to succinic anhydride. In certain embodimentssuch methods comprise an additional step of converting the succinicanhydride to a product selected from the group consisting of: succinicacid, 1,4 butanediol, tetrahydrofuran, gamma butyrolactone, or anycombination of two or more of these.

In certain embodiments where the method above further comprisesconverting beta propiolactone to succinic anhydride, the conversion isconducted in a second carbonylation reactor. In certain embodiments, thesecond carbonylation reactor is also fed with the syngas stream producedin step (a) where it is contacted with the beta propiolactone in thepresence of a carbonylation catalyst to deplete the syngas of at least aportion of its CO content and provide succinic anhydride as a secondcarbonylation product. In certain embodiments, a second upgraded syngasstream, characterized in that it has a higher H₂ to CO ratio that thesyngas stream produced in step (a) is recovered from the secondcarbonylation reactor. In certain embodiments, the first and secondupgraded syngas streams are combined and utilized in step (d).

In certain embodiments where the method above further comprisesconverting beta propiolactone to succinic anhydride, the conversion isconducted in a second carbonylation reactor which is fed with theupgraded syngas stream produced in step (b) where it is contacted withthe beta propiolactone in the presence of a carbonylation catalyst tofurther deplete the upgraded syngas stream of its CO thereby providing atwice-upgraded syngas stream having a higher H₂ to CO ratio than theupgraded syngas stream from step (c). In certain embodiments, the methodfurther comprises recovering the twice upgraded syngas stream from thesecond carbonylation reactor and feeding it to the methanol reactor instep (d).

It should generally be understood that reference to “a first reactionzone” and “a second reaction zone”, etc. or “a first reactor” and “asecond reactor”, etc., or “a first stream” and “a second stream”, etc.,does not necessarily imply an order of the reaction zones, reactors orstreams. In some variations, the use of such references denotes thenumber of reaction zones, reactors or streams present. In othervariations, an order may be implied by the context in which the reactionzones, reactors or streams are configured or used.

In certain embodiments, the product of step (b) of the method above ispolypropiolactone and the method further comprises pyrolyzing thepolypropiolactone to produce acrylic acid.

In certain embodiments, the carbonylation catalyst in step (b) of themethod above comprises a metal carbonyl compound. In certainembodiments, the metal carbonyl compound is selected from any of thosedescribed herein. In certain embodiments, the metal carbonyl compoundcomprises a cobalt carbonyl compound. In certain embodiments, metalcarbonyl compound comprises a rhodium carbonyl compound. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises a metal carbonyl compound in combination with anothercomponent selected from the group consisting of: organic bases, neutralLewis acids, and cationic Lewis acids. In certain embodiments, thecarbonylation catalyst in step (b) of the method above comprises ananionic cobalt carbonyl compound in combination with a cationic Lewisacid. In certain embodiments, such cationic Lewis acids comprise metalligand complexes. In certain embodiments, the metal ligand complexescomprise any complex described herein. In certain embodiments, suchmetal ligand complexes comprise a metal atom coordinated to amultidentate ligand. In certain embodiments, such metal ligand complexescomprise an aluminum or chromium atom. In certain embodiments, suchmetal ligand complexes comprise a porphyrin or salen ligand. In certainembodiments, the carbonylation catalyst in step (b) of the method abovecomprises any combination of a metal carbonyl compound and a metalcomplex, as described herein.

In certain embodiments, step (c) in the method above is characterized inthat the upgraded syngas stream recovered has an H₂ to CO ratio betweenabout 1.2:1 and about 3:1. In certain embodiments, the upgraded syngasstream recovered has an H₂ to CO ratio between about 1.6:1 and about2.8:1, between about 1.8:1 and about 2.6:1, between about 1.8:1 andabout 2.2:1, or between about 1.9:1 and about 2.1:1. In certainembodiments, the upgraded syngas stream recovered has an H₂ to CO ratioof about 2:1.

In certain embodiments, the method above is characterized in that thereaction pressure in the carbonylation reactor is higher than thereaction pressure in the methanol synthesis reactor. In certainembodiments, the upgraded syngas stream is fed to the methanol synthesisreactor without an intermediate compression step. In certainembodiments, the upgraded syngas stream exits the carbonylation reactorvia a backpressure regulator and is fed directly to the methanolsynthesis reactor.

In certain embodiments, the method above is characterized in that theupgraded syngas stream is treated to remove one or more components priorto use in the methanol synthesis step. In certain embodiments, theupgraded syngas stream is treated to remove residual solvent prior tofeeding the stream to the methanol synthesis reactor. In certainembodiments, the upgraded syngas stream is treated to remove residualepoxide prior to feeding the stream to the methanol synthesis reactor.In certain embodiments, the upgraded syngas stream is treated to removecarbon dioxide prior to feeding the stream to the methanol synthesisreactor.

In certain embodiments, the method above is characterized in that themethanol synthesis reactor in step (d) utilizes a catalyst comprisingone or more of, copper, alumina and zinc oxide.

In certain embodiments, the method above further comprises feedingmethanol produced in the methanol reactor to an MTO reactor where it isconverted to olefins. In certain embodiments, the MTO reactor convertsthe methanol to ethylene, propylene or a mixture of ethylene andpropylene.

In embodiments where the process is integrated to an MTO reactor, thepossibility exists for a process that produces carbonylation productsderived entirely from the carbon source fed to the syngas productionstep. This is achieved by utilizing ethylene or propylene from the MTOstage to produce ethylene oxide or propylene oxide which is thenutilized as the feedstock for the carbonylation reactor.

Therefore, in certain embodiments, provided are methods for theproduction of 100% biomass-derived chemicals. In certain embodiments,such chemicals are the result of the process depicted in FIG. 5. FIG. 5shows an integrated process for production of acrylic acid from biomass.As shown, biomass is gasified in Gasifier 101 to produce a syngas stream101 having an H₂:CO ratio less than 1 (typically 0.5-0.7:1). This is fedto Carbonylation Reactor 200 where it is contacted with ethylene oxidein the presence of carbonylation catalyst. Carbonylation reactorproduces beta propiolactone stream 209 along with upgraded syngas stream210. Upgraded syngas stream 210 has an H2 to CO ratio around 2:1 and istherefore suitable for use in methanol synthesis reactor 600. Themethanol from reactor 600 is fed to MTO reactor 700 where it isconverted to ethylene stream 212 (and optionally additional streams suchas propylene and higher olefins, not shown). Ethylene stream 212 isdirected to an oxidation reactor 800 where it is converted to ethyleneoxide. The resulting ethylene oxide is fed to carbonylation reactor 200to react with syngas stream 101.

To complete the acrylic acid synthesis the beta lactone stream 209 fromthe carbonylation reactor is fed to AA reactor 900 where it is convertedto acrylic acid. The three carbon atoms in the resulting AA are allderived from the biomass fed to reactor 101

In one aspect, provided is acrylic acid wherein all three carbon atomsare derived from biomass in an integrated gasification processcharacterized in that the carboxylic carbon atom is derived from CO inthe syngas, and the two ethylene carbon atoms are derived from ethyleneproduced by MTO utilizing methanol formed from a syngas stream upgradedto increase its H₂ content by carbonylation of the epoxide.

A closely related process provides biomass derived polymers such aspolypropiolactone (PPL) or poly(3-hydroxybutyrolactone) (PHB). Suchprocesses either add a beta lactone polymerization reactor fed by thebeta lactone stream, or utilize conditions in the carbonylation reactorto produce polyester as the primary product. For the PHB process, theMTO reactor would be operated to provide a propylene stream which isthen oxidized to propylene oxide which is fed to the carbonylationreactor.

In certain other embodiments, provided are methods for the production of100% biomass-derived C4 chemicals. In certain embodiments such chemicalsare the result of the process depicted in FIG. 6. FIG. 6 shows anintegrated process for production of acrylic acid from biomass. Asshown, biomass is gasified in Gasifier 101 to produce a syngas stream101 having an H₂:CO ratio less than 1 (typically 0.5-0.7:1). This is fedto Carbonylation Reactor 200 where it is contacted with ethylene oxidein the presence of carbonylation catalyst. Carbonylation reactorproduces beta propiolactone stream 209 along with upgraded syngas stream210. Upgraded syngas stream 210 has an H₂ to CO ratio around 2:1 and istherefore suitable for use in methanol synthesis reactor 600. Themethanol from reactor 600 is fed to MTO reactor 700 where it isconverted to ethylene stream 212 (and optionally additional streams suchas propylene and higher olefins, not shown). Ethylene stream 212 isdirected to an oxidation reactor 800 where it is converted to ethyleneoxide. The resulting ethylene oxide is fed to carbonylation reactor 200to react with syngas stream 101. To complete the C4 chemicals synthesis,the beta lactone stream 209 from the carbonylation reactor is fed to2^(nd) carbonylation reactor 202 where it is converted to succinicanhydride. Succinic anhydride stream 214 is fed to hydrogenation reactorwhere it is converted to C4 commodity chemicals such as 1,4 butanediol,tetrahydrofuran, GBL, or combinations of two or more of these. The threecarbon atoms in the resulting chemicals are all derived from the biomassfed to reactor 101:

In one aspect, provided are C4 chemicals (such as THF, BDO and/or GBL)wherein all four carbon atoms are derived from biomass in an integratedgasification process characterized in that the carbon atoms boned tooxygen atoms are derived from CO in syngas, and the two other carbonatoms are derived from ethylene produced by MTO utilizing methanolformed from a syngas stream upgraded to increase its H₂ content bycarbonylation of the epoxide.

In certain embodiments, the method above is characterized in that theoverall process has a carbon efficiency greater than 50%. That is, atleast 50% of the carbon atoms fed to the syngas production step arecontained in the combined products from the EO carbonylation reactor andthe methanol synthesis reactor. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencygreater than 55%, greater than 60%, greater than 62%, greater than 63%,greater than 64%, or greater than 65%. In certain embodiments, themethod is characterized in that the overall process has a carbonefficiency greater than 66%, greater than 67%, greater than 68%, greaterthan 69%, or greater than 70%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 50% and about 60%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 55% and about 60%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 60% and about 64%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 64% and about 67%. In certain embodiments, the method ischaracterized in that the overall process has a carbon efficiencybetween about 67% and about 70%.

In certain embodiments, the method above is characterized in that themethanol synthesis process in step (d) is fed with syngas from thegasification process in step (a) without utilizing the water gas shiftreaction to increase its H₂ to CO ratio.

VIII) Production of EO Carbonylation Products Having Variable Bio-BasedContent

While the foregoing has focused on the use of various bio-based andfossil feedstocks for the integrated production of EO carbonylationproducts together with other products, the EO carbonylation technologydescribed herein is uniquely suited for the integration of EO and COfrom both bio-based and fossil sources to create EO carbonylationproducts containing carbon from both sources. In some embodiments, it isdesirable for economic or technical reasons to have the flexibility toproduce EO carbonylation products derived from both bio-based and fossilsources. The processes described herein for producing 100% bio-basedcontent are also applicable to the production of EO carbonylationproducts having between 0% to 100%, (non-inclusive) bio-based content.

In such embodiments, the resulting EO carbonylation products, includingbeta propiolactone, and succinic anhydride may feature one or bothcarbonyl carbons derived from bio-based or fossil sources, and thenon-carbonyl carbons derived from bio-based or fossil sources.

In some embodiments, provided is an EO carbonylation product where eachcarbonyl carbon is derived from a bio-based source, and the twonon-carbonyl carbons are derived from a fossil source. In someembodiments, provided is an EO carbonylation product where each carbonylcarbon is derived from a fossil source, and the two non-carbonyl carbonsare derived from a bio-based source. In some embodiments, provided is anEO carbonylation product where one carbonyl carbon is derived from abio-based source, another carbonyl carbon is derived from fossil source,and the two non-carbonyl carbons are derived from a fossil source. Insome embodiments, provided is an EO carbonylation product where onecarbonyl carbon is derived from a bio-based source, another carbonylcarbon is derived from fossil source, and the two non-carbonyl carbonsare derived from a bio-based source.

In one aspect, provided is beta propiolactone, wherein the betapropiolactone has three carbon atoms, and wherein two of the threecarbon atoms in the beta propiolactone are bio-based and the thirdcarbon atom is fossil-based. In some variations, the carbonyl carbon ofthe beta propiolactone is fossil-based.

In another aspect, provided is beta propiolactone, wherein the betapropiolactone has three carbon atoms, and wherein one of the threecarbon atoms in the beta propiolactone is bio-based and the other twocarbons atom are fossil-based. In some variations, the carbonyl carbonof the beta propiolactone is bio-based.

In yet another aspect, provided is succinic anhydride, wherein thesuccinic anhydride has four carbon atoms, and wherein two of the fourcarbon atoms of the succinic anhydride are bio-based and two of thecarbon atoms are fossil-based. In some variations, the two carbonylcarbon atoms of the succinic anhydride are bio-based. In othervariations, the two carbonyl carbon atoms of the succinic anhydride arefossil-based.

Examples of bio-based sources for ethylene oxide include, for example,biomass fermentation or municipal solid waste (MSW) gasification toproduce ethanol which is further processed to ethylene oxide. Examplesof bio-based sources of carbon monoxide include, for example, MSWgasification to produce methanol that is further processed to carbonmonoxide, or electrolysis of carbon dioxide.

Examples of fossil sources for ethylene oxide include, for example,naphtha, shale gas, and coal, which can be cracked to produce ethylene,which is further processed to ethylene oxide. Examples of fossil sourcesfor carbon monoxide include, for example, coal, oil, and shale gas,which can be processed into syngas (comprising carbon monoxide).

IX) Determination of Bio-Based Content of EO Carbonylation Products andSource Materials

Bio-based content: the bio-based content of a material may be measuredusing the ASTM D6866 method, which allows the determination of thebio-based content of materials using radiocarbon analysis by acceleratormass spectrometry, liquid scintillation counting, and isotope massspectrometry. When nitrogen in the atmosphere is struck by anultraviolet light produced neutron, it loses a proton and forms carbonthat has a molecular weight of 14, which is radioactive. This ¹⁴C isimmediately oxidized into carbon dioxide, and represents a small, butmeasurable fraction of atmospheric carbon. Atmospheric carbon dioxide iscycled by green plants to make organic molecules during photosynthesis.The cycle is completed when the green plants or other forms of lifemetabolize the organic molecules producing carbon dioxide which is thenable to return back to the atmosphere. Virtually all forms of life onEarth depend on this green plant production of organic molecules toproduce the chemical energy that facilitates growth and reproduction.Therefore, the ¹⁴C that exists in the atmosphere becomes part of alllife forms and their biological products. These renewably based organicmolecules that biodegrade to carbon dioxide do not contribute to globalwarming because no net increase of carbon is emitted to the atmosphere.In contrast, fossil fuel-based carbon does not have the signatureradiocarbon ratio of atmospheric carbon dioxide. See WO 2009/155086.

The application of ASTM D6866 to derive a “bio-based content” is builton the same concepts as radiocarbon dating, but without use of the ageequations. The analysis is performed by deriving a ratio of the amountof radiocarbon (¹⁴C) in an unknown sample to that of a modern referencestandard. The ratio is reported as a percentage, with the units “pMC”(percent modern carbon). If the material being analyzed is a mixture ofpresent day radiocarbon and fossil carbon (containing no radiocarbon),then the pMC value obtained correlates directly to the amount ofbio-based material present in the sample. The modern reference standardused in radiocarbon dating is a NIST (National Institute of Standardsand Technology) standard with a known radiocarbon content equivalentapproximately to the year AD 1950. The year AD 1950 was chosen becauseit represented a time prior to thermonuclear weapons testing whichintroduced large amounts of excess radiocarbon into the atmosphere witheach explosion (termed “bomb carbon”). The AD 1950 reference represents100 pMC. “Bomb carbon” in the atmosphere reached almost twice normallevels in 1963 at the peak of testing and prior to the treaty haltingthe testing. Its distribution within the atmosphere has beenapproximated since its appearance, showing values that are greater than100 pMC for plants and animals living since AD 1950. The distribution ofbomb carbon has gradually decreased over time, with today's value beingnear 107.5 pMC. As a result, a fresh biomass material, such as corn,could result in a radiocarbon signature near 107.5 pMC.

Petroleum-based carbon does not have the signature radiocarbon ratio ofatmospheric carbon dioxide. Research has noted that fossil fuels andpetrochemicals have less than about 1 pMC, and typically less than about0.1 pMC, for example, less than about 0.03 pMC. However, compoundsderived entirely from renewable resources have at least about 95 percentmodern carbon (pMC), they may have at least about 99 pMC, includingabout 100 pMC.

Combining fossil carbon with present day carbon into a material willresult in a dilution of the present day pMC content. By presuming that107.5 pMC represents present day bio-based materials and 0 pMCrepresents petroleum derivatives, the measured pMC value for thatmaterial will reflect the proportions of the two component types. Amaterial derived 100% from present day biomass would give a radiocarbonsignature near 107.5 pMC. If that material were diluted with 50%petroleum derivatives, it would give a radiocarbon signature near 54pMC.

A bio-based content result is derived by assigning 100% equal to 107.5pMC and 0% equal to 0 pMC. In this regard, a sample measuring 99 pMCwill give an equivalent bio-based content result of 93%.

Assessment of the materials described herein according to the presentembodiments is performed in accordance with ASTM D6866 revision 12 (i.e.ASTM D6866-12). In some embodiments, the assessments are performedaccording to the procedures of Method B of ASTM-D6866-12. The meanvalues encompass an absolute range of 6% (plus and minus 3% on eitherside of the bio-based content value) to account for variations inend-component radiocarbon signatures. It is presumed that all materialsare present day or fossil in origin and that the desired result is theamount of bio-based carbon “present” in the material, not the amount ofbio-material “used” in the manufacturing process.

Other techniques for assessing the bio-based content of materials aredescribed in U.S. Pat. Nos. 3,885,155, 4,427,884, 4,973,841, 5,438,194,and 5,661,299, and WO2009/155086.

For example, BPL contains three carbon atoms in its structural unit. Ifthe BPL is produced using EO and CO both from a bio-based source, thenit theoretically has a bio-based content of 100%, and a pMC of 107.5,because all of the carbon atoms are derived from a renewable resource.

In some embodiments, if the BPL is produced using EO from 100% bio-basedsources and CO from a fossil source, then it theoretically has abio-based content of about 66.7% and a pMC of about 71.7, as two-thirdsof the carbon atoms in the resulting BPL are derived from a bio-basedsource. In some embodiments, if the BPL is produced using EO from afossil source, and CO from a bio-based source, then it theoretically hasa bio-based content of about 33.3% and a pMC of about 35.8, as onlyone-third of the carbon atoms in the resulting BPL are derived from abio-based source.

In some embodiments, if succinic anhydride is produced using EO from100% bio-based sources and CO from 100% fossil sources, then ittheoretically has a bio-based content of about 50% and a pMC of about54, because half of the four carbon atoms in the resulting SA arederived from a bio-based source. In some embodiments, if succinicanhydride is produced using EO from 100% bio-based sources and oneequivalent of CO from bio-based sources and one equivalent of CO fromfossil sources, then it theoretically has a bio-based content of about75% and a pMC of about 80, because three-quarters of the carbon atoms inthe resulting SA are derived from a bio-based source. In someembodiments, if succinic anhydride is produced using EO from 100% fossilsources and one equivalent of CO from bio-based sources and oneequivalent of CO from fossil sources, then it theoretically has abio-based content of about 25% and a pMC of about 27, becauseone-quarter of the carbon atoms in the resulting SA are derived from abio-based source.

The calculations used in the embodiments above assume that all of the EOor CO used in a given reaction step in the production of EOcarbonylation products is either entirely derived from either bio-basedor fossil sources. However, the methods described herein alsocontemplate wherein some of the EO or CO used in a given reaction stepin the production of EO carbonylation products is derived from a mixtureof bio-based or fossil sources, representative embodiments of whichfollow.

In some embodiments, if BPL is produced using EO from 50% bio-basedsources and 50% fossil sources and CO from 25% bio-based sources and 75%fossil sources, then it theoretically has a bio-based content of about41.2% and a pMC of about 44.8, as two-thirds of the carbon atoms in theresulting BPL are derived from a bio-based source.

Such a flexible system allows for the production of EO carbonylationproducts (and their downstream products, such as acrylic acid),containing a finely tunable percentage of bio-based material. Forexample, if it is important to meet certain percentages of bio-basedmaterial in BPL, but the price of one bio-based feedstock (e.g. EO) isprohibitively expensive due to market shortages, the percentage ofbio-based CO can be increased to provide the same overall percentage inthe final BPL product.

Traditional methods for determining the bio-based content of a sample ofBPL or SA (such as those described in Methods B and C of ASTM D6866),require the complete combustion or conversion of the sample to eithercarbon dioxide or benzene, which are then analyzed by mass spectrometryor scintillation counting. This allows for the calculation of theoverall aggregate bio-based content of the feedstocks used to producethe carbonylation products, but results in the loss of the ability todetermine the bio-based content of the EO and CO feedstocks themselves.Such knowledge is useful for many reasons, including, for example, tothe forensic determination of the source of a given sample of product.

A synthon is a chemical structural unit that provides one or more atomspresent in the molecular structure of a product molecule. In the case ofBPL or SA produced by carbonylation of EO, CO is the synthon thatprovides each of the carbonyl groups of BPL and SA, and EO is thesynthon that provides each of the methylene (CH₂) carbons in BPL and SA.By extension, polypropiolactone (PPL), acrylic acid (AA), andpolyacrylic acid made from BPL by this method can also be said to havetheir respective carbonyl carbons derived from the CO synthon, and theirnon-carbonyl carbons derived from the EO synthon.

In some embodiments, provided is a method for determining the bio-basedcontent of the feedstocks by selectively degrading a sample of BPL orSA, comprising the mono-decarboxylation of the sample.

In the case of BPL, thermal decarboxylation results in the decyclizationof BPL to ethylene and carbon dioxide, the ethylene fragment comprisingthe two carbons initially derived from EO, and the carbon dioxidecomprising the one carbon initially derived from CO. Thus, the carbondioxide produced by decarboxylation can be analyzed by methods such asAccelerator Mass Spectrometry (AMS) and Isotope Ratio Mass Spectrometry(IRMS) to determine the isotopic abundance of ¹⁴C in the carbon dioxide,and by proxy in the CO. The ethylene can then be analyzed directly, orfurther combusted to carbon dioxide, then analyzed, to determine thebio-based content of the EO used to produce the BPL.

In one embodiment, provided is a method for determining whether a sampleof beta-propiolactone was produced from a combination of bio-based andfossil carbon synthons, comprising:

(i) thermally decomposing the sample to ethylene and carbon dioxide;

(ii) determining the isotopic abundance of ¹⁴C in the carbon dioxidecarbon;

(iii) determining the isotopic abundance of ¹⁴C in C the ethylenecarbons;

wherein, if the isotopic abundances in (ii) and (iii) are not equal, thebeta-propiolactone was produced from a combination of bio-based andfossil carbon synthons.

14 In some embodiments, the isotopic abundance of C is determined byASTM D6866.

In the case of SA, thermal decarboxylation (which may be catalyzed bybasic conditions), results in the spiro-decarboxylation of two moleculesof SA to one molecule of γ-ketopimelic acid, and one molecule of carbondioxide, which can be analyzed as in the previous paragraph to determinethe bio-based content of the CO used to produce the SA. Theγ-ketopimelic acid can then be combusted to carbon dioxide and analyzedto determine the bio-based content of the EO used to produce the BPL,taking into consideration that three of the seven carbons in theγ-ketopimelic acid are derived from CO. This is possible, as thebio-based content of the CO is already known from the initialdecarboxylation, and so the bio-based content attributable to the EO canbe determined by simple algebra.

In some embodiments, provided is a method for determining whether asample of succinic anhydride was produced from a combination ofbio-based and fossil carbon synthons, comprising:

(i) thermally decomposing the sample to γ-ketopimelic acid and carbondioxide;

(ii) determining the isotopic abundance of ¹⁴C in the carbon dioxidecarbon;

(iii) determining the isotopic abundance of ¹⁴C in the γ-ketopimelicacid carbons;

wherein, if the isotopic abundances in (ii) and (iii) are not equal, thesuccinic anhydride was produced from a combination of bio-based andfossil carbon synthons.

When polyacrylic acid is heated to between 103 and 216° C. in thepresence of a catalyst (copper nitrate is preferred) under an inert(preferably argon) atmosphere, it decomposes to carbon dioxide and aresidue comprising a complex mixture of degradation products. SeeDubinsky, et al. Polymer Degradation and Stability 86 (2004) 171-178.The exact composition of this mixture of degradation products in theresidue is not important. The carbon dioxide liberated in thisnon-combustive decarboxylation can be analyzed as in the previousparagraphs to determine the bio-based content of the CO used to producethe polyacrylic acid. The residual degradation products are completelycombusted to carbon dioxide which can then analyzed to determine theisotopic abundance of ¹⁴C. While not as exact as the procedures abovefor BPL and SA, a comparison of the carbon isotopic ratios for thecarbon dioxide liberated during decarboxyation and that obtained fromthe combustion of the degradation products provides an answer as towhether the polyacrylic acid polymer was produced from a combination ofbio-based and fossil carbon synthons.

In some embodiments, provided is a method for determining whether asample of polyacrylic acid was produced from a combination of bio-basedand fossil carbon synthons, comprising:

(i) thermally decomposing the sample in the presence of a coppercatalyst at a temperature between 103 and 216° C. to carbon dioxide anda residue;

(ii) determining the isotopic abundance of ¹⁴C in the carbon dioxidecarbon; and

(iii) determining the isotopic abundance of ¹⁴C in C the residue, and

wherein, if the isotopic abundances in (ii) and (iii) are not equal, thepolyacrylic acid was produced from a combination of bio-based and fossilcarbon synthons.

Metal Carbonyl Compounds

In certain embodiments, metal carbonyl compound that may be used in themethods described herein comprises an anionic metal carbonyl moiety. Inother embodiments, the metal carbonyl compound comprises a neutral metalcarbonyl compound. In certain embodiments, the metal carbonyl compoundcomprises a metal carbonyl hydride or a hydrido metal carbonyl compound.In some embodiments, the metal carbonyl compound acts as a pre-catalystwhich reacts in situ with one or more reaction components to provide anactive species different from the compound initially provided. Suchpre-catalysts are specifically encompassed herein, as it is recognizedthat the active species in a given reaction may not be known withcertainty; thus the identification of such a reactive species in situdoes not itself depart from the spirit or teachings herein.

In certain embodiments, the metal carbonyl compound comprises an anionicmetal carbonyl species. In certain embodiments, such anionic metalcarbonyl species have the general formula [Q_(d)M′_(e)(CO)_(w)]^(y−),where Q is any ligand and need not be present, M′ is a metal atom, d isan integer between 0 and 8 inclusive, e is an integer between 1 and 6inclusive, w is a number such as to provide the stable anionic metalcarbonyl complex, and y is the charge of the anionic metal carbonylspecies. In certain embodiments, the anionic metal carbonyl has thegeneral formula [QM′(CO)_(w)]^(y−), where Q is any ligand and need notbe present, M′ is a metal atom, w is a number such as to provide thestable anionic metal carbonyl, and y is the charge of the anionic metalcarbonyl.

In certain embodiments, the anionic metal carbonyl species includemonoanionic carbonyl complexes of metals from groups 5, 7 or 9 of theperiodic table or dianionic carbonyl complexes of metals from groups 4or 8 of the periodic table. In some embodiments, the anionic metalcarbonyl compound contains cobalt or manganese. In some embodiments, theanionic metal carbonyl compound contains rhodium. Suitable anionic metalcarbonyl compounds include, for example, [Co(CO)₄]⁻, [Ti(CO)₆]²⁻,[V(CO)₆]⁻, [Rh(CO)₄]⁻, [Fe(CO)₄]²⁻, [Ru(CO)₄]²⁻, [Os(CO)₄]²⁻,[Cr₂(CO)₁₀]²⁻, [Fe₂(CO)₈]²⁻, [Tc(CO)₅]⁻, [Re(CO)₅]⁻, and [Mn(CO)₅]⁻. Insome embodiments, the anionic metal carbonyl comprises [Co(CO)₄]⁻. Insome embodiments, a mixture of two or more anionic metal carbonylcomplexes may be present in the polymerization system.

The term “such as to provide a stable anionic metal carbonyl” for[Q_(d)M′_(e)(CO)_(w)]^(y−) is used herein to mean that[Q_(d)M′_(e)(CO)_(w)]^(y−) is a species that may be characterized byanalytical means, e.g., NMR, IR, X-ray crystallography, Ramanspectroscopy and/or electron spin resonance (EPR) and isolable incatalyst form in the presence of a suitable cation or a species formedin situ. It is to be understood that metals which can form stable metalcarbonyl complexes have known coordinative capacities and propensitiesto form polynuclear complexes which, together with the number andcharacter of optional ligands Q that may be present and the charge onthe complex will determine the number of sites available for CO tocoordinate and therefore the value of w. Typically, such compoundsconform to the “18-electron rule”. Such knowledge is within the grasp ofone having ordinary skill in the arts pertaining to the synthesis andcharacterization of metal carbonyl compounds.

In embodiments where the metal carbonyl compound is an anionic species,one or more cations must also necessarily be present. The presentdisclosure places no particular constraints on the identity of suchcations. For example, in certain embodiments, the metal carbonyl anionis associated with a cationic Lewis acid. In other embodiments a cationassociated with a provided anionic metal carbonyl compound is a simplemetal cation such as those from Groups 1 or 2 of the periodic table(e.g. Na⁺, Li⁺, K⁺, and Mg²⁺). In other embodiments a cation associatedwith a provided anionic metal carbonyl compound is a bulky nonelectrophilic cation such as an ‘onium salt’ (e.g. Bu₄N⁺, PPN⁺, Ph₄P⁺,and Ph₄As⁺). In other embodiments, a metal carbonyl anion is associatedwith a protonated nitrogen compound (e.g., a cation may comprise acompound such as MeTBD-H⁺, DMAP-H⁺, DABCO-H⁺, and DBU-H⁺). In someembodiments, compounds comprising such protonated nitrogen compounds areprovided as the reaction product between an acidic hydrido metalcarbonyl compound and a basic nitrogen-containing compound (e.g., amixture of DBU and HCo(CO)₄).

In certain embodiments, the metal carbonyl compound comprises a neutralmetal carbonyl. In certain embodiments, such neutral metal carbonylcompounds have the general formula Q_(d)M′_(e)(CO)_(w′), where Q is anyligand and need not be present, M′ is a metal atom, d is an integerbetween 0 and 8 inclusive, e is an integer between 1 and 6 inclusive,and w′ is a number such as to provide the stable neutral metal carbonylcomplex. In certain embodiments, the neutral metal carbonyl has thegeneral formula QM′(CO)_(w′). In certain embodiments, the neutral metalcarbonyl has the general formula M′(CO)_(w′). In certain embodiments,the neutral metal carbonyl has the general formula QM′₂(CO)_(w′). Incertain embodiments, the neutral metal carbonyl has the general formulaM′₂(CO)_(w′). Suitable neutral metal carbonyl compounds include, forexample, Ti(CO)₇, V₂(CO)₁₂, Cr(CO)₆, Mo(CO)₆, W(CO)₆, Mn₂(CO)₁₀,Tc₂(CO)₁₀, Re₂(CO)₁₀, Fe(CO)₅, Ru(CO)₅, Os(CO)₅, Ru₃(CO)₁₂,Os₃(CO)₁₂Fe₃(CO)₁₂, Fe₂(CO)₉, Co₄(CO)₁₂, Rh₄(CO)₁₂, Rh₆(CO)₁₆,Ir₄(CO)₁₂, Co₂(CO)₈, and Ni(CO)₄.

The term “such as to provide a stable neutral metal carbonyl forQ_(d)M′_(e)(CO)_(w′) is used herein to mean that Q_(d)M′_(e)(CO)_(w′) isa species that may be characterized by analytical means, e.g., NMR, IR,X-ray crystallography, Raman spectroscopy and/or electron spin resonance(EPR) and isolable in pure form or a species formed in situ. It is to beunderstood that metals which can form stable metal carbonyl complexeshave known coordinative capacities and propensities to form polynuclearcomplexes which, together with the number and character of optionalligands Q that may be present will determine the number of sitesavailable for CO to coordinate and therefore the value of w′. Typically,such compounds conform to stoichiometries conforming to the “18-electronrule”. Such knowledge is within the grasp of one having ordinary skillin the arts pertaining to the synthesis and characterization of metalcarbonyl compounds.

In certain embodiments, one or more of the CO ligands of any of themetal carbonyl compounds described above is replaced with a ligand Q. Incertain embodiments, Q is a phosphine ligand. In certain embodiments, Qis a triaryl phosphine. In certain embodiments, Q is trialkyl phosphine.In certain embodiments, Q is a phosphite ligand. In certain embodiments,Q is an optionally substituted cyclopentadienyl ligand. In certainembodiments, Q is cp. In certain embodiments, Q is cp*.

In certain embodiments, polymerization systems described herein comprisehydrido metal carbonyl compounds. In certain embodiments, such compoundsare provided as the hydrido metal carbonyl compound, while in otherembodiments, the hydrido metal carbonyl is generated in situ by reactionwith hydrogen gas, or with a protic acid using methods known in the art(see for example Chem. Rev., 1972, 72 (3), pp 231-281 DOI:10.1021/cr60277a003).

In certain embodiments, the hydrido metal carbonyl (either as providedor generated in situ) comprises one or more of HCo(CO)₄, HCoQ(CO)₃,HMn(CO)₅, HMn(CO)₄Q, HW(CO)₃Q, HRe(CO)₅, HMo(CO)₃Q, HOs(CO)₂Q,HMo(CO)₂Q₂, HFe(CO₂)Q, HW(CO)₂Q₂, HRuCOQ₂, H₂Fe(CO)₄ or H₂Ru(CO)₄, whereeach Q is independently as defined above and in the classes andsubclasses herein. In certain embodiments, the metal carbonyl hydride(either as provided or generated in situ) comprises HCo(CO)₄. In certainembodiments, the metal carbonyl hydride (either as provided or generatedin situ) comprises HCo(CO)₃PR₃, where each R is independently anoptionally substituted aryl group, an optionally substituted C₁₋₂₀aliphatic group, an optionally substituted C₁₋₁₀ alkoxy group, or anoptionally substituted phenoxy group. In certain embodiments, the metalcarbonyl hydride (either as provided or generated in situ) comprisesHCo(CO)₃cp, where cp represents an optionally substituted pentadienylligand. In certain embodiments, the metal carbonyl hydride (either asprovided or generated in situ) comprises HMn(CO)₅. In certainembodiments, the metal carbonyl hydride (either as provided or generatedin situ) comprises H₂Fe(CO)₄.

In certain embodiments, for any of the metal carbonyl compoundsdescribed above, M′ comprises a transition metal. In certainembodiments, for any of the metal carbonyl compounds described above, M′is selected from Groups 5 (Ti) to 10 (Ni) of the periodic table. Incertain embodiments, M′ is a Group 9 metal. In certain embodiments, M′is Co. In certain embodiments, M′ is Rh. In certain embodiments, M′ isIr. In certain embodiments, M′ is Fe. In certain embodiments, M′ is Mn.

Lewis Acidic Metal Complexes

In certain embodiments where a carbonylation catalyst is utilized in anyof the methods above, the carbonylation catalyst comprises a metalcarbonyl compound in combination with a cationic Lewis acid, the Lewisacid has a formula [(L^(c))_(v)M_(b)]^(z+), wherein:

L^(c) is a ligand where, when two or more L^(c) are present, each may bethe same or different;

M is a metal atom where, when two M are present, each may be the same ordifferent;

v is an integer from 1 to 4 inclusive;

b is an integer from 1 to 2 inclusive; and

z is an integer greater than 0 that represents the cationic charge onthe metal complex.

In certain embodiments, the Lewis acids conform to structure I:

wherein:

is a multidentate ligand;

M is a metal atom coordinated to the multidentate ligand;

a is the charge of the metal atom and ranges from 0 to 2; and

In certain embodiments, provided metal complexes conform to structureII:

wherein a is as defined above (each a may be the same or different), and

M¹ is a first metal atom;

M² is a second metal atom;

comprises a multidentate ligand system capable of coordinating bothmetal atoms.

For sake of clarity, and to avoid confusion between the net and totalcharge of the metal atoms in complexes I and II and other structuresherein, the charge (a⁺) shown on the metal atom in complexes I and IIabove represents the net charge on the metal atom after it has satisfiedany anionic sites of the multidentate ligand. For example, if a metalatom in a complex of formula I were Cr(III), and the ligand wereporphyrin (a tetradentate ligand with a charge of −2), then the chromiumatom would have a net charge of +1, and a would be 1.

Suitable multidentate ligands include, for example, porphyrin ligands 1,salen ligands 2, dibenzotetramethyltetraaza[14]annulene (tmtaa) ligands3, phthalocyaninate ligands 4, Trost ligand 5, tetraphenylporphyrinligands 6, and corrole ligands 7. In certain embodiments, themultidentate ligand is a salen ligands. In other embodiments, themultidentate ligand is a porphyrin ligands. In other embodiments, themultidentate ligand is a tetraphenylporphyrin ligands. In otherembodiments, the multidentate ligand is a corrole ligands. Any of theforegoing ligands can be unsubstituted or can be substituted. Numerousvariously substituted analogs of these ligands are known in the art andwill be apparent to the skilled artisan.

wherein each of R^(c), R^(d), R^(a), R^(1a), R^(2a), R^(3a), R^(1a′),R^(2a′), R^(3a′), and M, is as defined and described in the classes andsubclasses herein.

In certain embodiments, Lewis acids provided in polymerization systemsdescribed herein comprise metal-porphinato complexes. In certainembodiments, the moiety

has the structure:

-   -   wherein each of M and a is as defined above and described in the        classes and subclasses herein, and    -   R^(d) at each occurrence is independently hydrogen, halogen,        —OR⁴, —NR^(y) ₂, —SR^(y), —CN, —NO₂, —SO₂R^(y), —SOR^(y),        —SO₂NR^(y) ₂; —CNO, —NR^(y)SO₂R^(y), —NCO, —N₃, —SiR^(y) ₃; or        an optionally substituted group selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic having 1-4        heteroatoms independently selected from the group consisting of        nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to        10-membered heteroaryl having 1-4 heteroatoms independently        selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered        heterocyclic having 1-2 heteroatoms independently selected from        the group consisting of nitrogen, oxygen, and sulfur, where two        or more R^(d) groups may be taken together to form one or more        optionally substituted rings, where each R^(y) is independently        hydrogen, an optionally substituted group selected the group        consisting of acyl; carbamoyl, arylalkyl; 6- to 10-membered        aryl; C₁₋₁₂ aliphatic; C₁₋₁₂ heteroaliphatic having 1-2        heteroatoms independently selected from the group consisting of        nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl        having 1-4 heteroatoms independently selected from the group        consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered        heterocyclic having 1-2 heteroatoms independently selected from        the group consisting of nitrogen, oxygen, and sulfur; an oxygen        protecting group; and a nitrogen protecting group; two R^(y) on        the same nitrogen atom are taken with the nitrogen atom to form        an optionally substituted 4- to 7-membered heterocyclic ring        having 0-2 additional heteroatoms independently selected from        the group consisting of nitrogen, oxygen, and sulfur; and each        R⁴ independently is a hydroxyl protecting group or R^(y).

In certain embodiments, the moiety

has the structure:

where M, a and R^(d) are as defined above and in the classes andsubclasses herein.

In some embodiments, the carbonylation catalyst includes a carbonylcobaltate in combination with an aluminum porphyrin compound. In someembodiments, the carbonylation catalyst is [(TPP)Al(THF)₂][Co(CO)₄]where TPP stands for tetraphenylporphyrin and THF stands fortetrahydrofuran.

In certain embodiments, the moiety

has the structure:

where M, a and R^(d) are as defined above and in the classes andsubclasses herein.

In certain embodiments, Lewis acids included in polymerization systemsherein comprise metallo salenate complexes. In certain embodiments, themoiety

has the structure:

wherein:

-   -   M, and a are as defined above and in the classes and subclasses        herein.    -   R^(1a), R^(1a′), R^(2a), R^(2a′), R^(3a), and R^(3a′) are        independently hydrogen, halogen, —OR⁴, —NR^(y) ₂, —SR^(y), —CN,        —NO₂, —SO₂R^(y), —SOR^(y), —SO₂NR^(y) ₂; —CNO, —NRSO₂R^(y),        —NCO, —N₃, —SiR^(y) ₃; or an optionally substituted group        selected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀        heteroaliphatic having 1-4 heteroatoms independently selected        from the group consisting of nitrogen, oxygen, and sulfur; 6- to        10-membered aryl; 5- to 10-membered heteroaryl having 1-4        heteroatoms independently selected from nitrogen, oxygen, and        sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms        independently selected from the group consisting of nitrogen,        oxygen, and sulfur; wherein each R⁴, and R^(y) is independently        as defined above and described in classes and subclasses herein,    -   wherein any of (R^(2a′) and R^(3a′)), (R^(2a) and R^(3a)),        (R^(1a) and R^(2a)), and (R^(1a′) and R^(2a′)) may optionally be        taken together with the carbon atoms to which they are attached        to form one or more rings which may in turn be substituted with        one or more R groups; and    -   R^(4a) is selected from the group consisting of:

where

-   -   R^(c) at each occurrence is independently hydrogen, halogen,        —OR⁴, —NR^(y) ₂, —SR^(y), —CN, —NO₂, —SO₂R^(y), —SOR^(y),        —SO₂NR^(y) ₂; —CNO, —NR^(y)SO₂R^(y), —NCO, —N₃, —SiR^(y) ₃; or        an optionally substituted group selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic having 1-4        heteroatoms independently selected from the group consisting of        nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to        10-membered heteroaryl having 1-4 heteroatoms independently        selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered        heterocyclic having 1-2 heteroatoms independently selected from        the group consisting of nitrogen, oxygen, and sulfur;    -   where:        -   two or more R^(c) groups may be taken together with the            carbon atoms to which they are attached and any intervening            atoms to form one or more rings;        -   when two R^(c) groups are attached to the same carbon atom,            they may be taken together along with the carbon atom to            which they are attached to form a moiety selected from the            group consisting of: a 3- to 8-membered spirocyclic ring, a            carbonyl, an oxime, a hydrazone, an imine; and an optionally            substituted alkene;    -   Y is a divalent linker selected from the group consisting of:        —NR^(y)—, —N(R^(y))C(O)—, —C(O)NR^(y)—, —O—, —C(O)—, —OC(O)—,        —C(O)O—, —S—, —SO—, —SO₂—, —C(═S)—, —C(═NR^(y))—, —N═N—; a        polyether; a C₃ to C₈ substituted or unsubstituted carbocycle;        and a C₁ to C₈ substituted or unsubstituted heterocycle;    -   m′ is 0 or an integer from 1 to 4, inclusive;    -   q is 0 or an integer from 1 to 4, inclusive; and    -   x is 0, 1, or 2.

In certain embodiments, a provided Lewis acid comprises a metallo salencompound, as shown in formula Ia:

-   -   wherein each of M, R^(d), and a, is as defined above and in the        classes and subclasses herein,

represents is an optionally substituted moiety linking the two nitrogenatoms of the diamine portion of the salen ligand, where

is selected from the group consisting of a C₃-C₁₄ carbocycle, a C₆-C₁₀aryl group, a C₃-C₁₄ heterocycle, and a C₅-C₁₀ heteroaryl group; or anoptionally substituted C₂₋₂₀ aliphatic group, wherein one or moremethylene units are optionally and independently replaced by —NR^(y)—,—N(R^(y))C(O)—, —C(O)N(R^(y))—, —OC(O)N(R^(y))—, —N(R^(y))C(O)O—,—OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO₂—, —C(═S)—,—C(═NR^(y))—, —C(═NOR^(y))— or —N═N—.

In certain embodiments metal complexes having formula Ia above, at leastone of the phenyl rings comprising the salicylaldehyde-derived portionof the metal complex is independently selected from the group consistingof:

In certain embodiments, a provided Lewis acid comprises a metallo salencompound, conforming to one of formulae Va or Vb:

-   -   where M, a, R^(d), R^(1a), R^(3a), R^(1a′), R^(3a′), and

are as defined above and in the classes and subclasses herein.

In certain embodiments of metal complexes having formulae Va or Vb, eachR^(1a) and R^(3a) is, independently, optionally substituted C₁-C₂₀aliphatic.

In certain embodiments, the moiety

comprises an optionally substituted 1,2-phenyl moiety.

In certain embodiments, Lewis acids included in polymerization systemsherein comprise metal-tmtaa complexes. In certain embodiments, themoiety

has the structure:

-   where M, a and R^(d) are as defined above and in the classes and    subclasses herein, and-   R^(e) at each occurrence is independently hydrogen, halogen, —OR⁴,    —NR^(y) ₂, —SR^(y), —CN, —NO₂, —SO₂R^(y), —SOR^(y), —SO₂NR^(y) ₂;    —CNO, —NR^(y)SO₂R^(y), —NCO, —N₃, —SiR^(y) ₃; or an optionally    substituted group selected from the group consisting of C₁₋₂₀    aliphatic; C₁₋₂₀ heteroaliphatic having 1-4 heteroatoms    independently selected from the group consisting of nitrogen,    oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered    heteroaryl having 1-4 heteroatoms independently selected from    nitrogen, oxygen, and sulfur; and 4- to 7-membered heterocyclic    having 1-2 heteroatoms independently selected from the group    consisting of nitrogen, oxygen, and sulfur.

In certain embodiments, the moiety

has the structure:

-   -   where each of M, a, R^(c) and R^(d) is as defined above and in        the classes and subclasses herein.

In certain embodiments, where polymerization systems herein include aLewis acidic metal complex, the metal atom is selected from the periodictable groups 2-13, inclusive. In certain embodiments, M is a transitionmetal selected from the periodic table groups 4, 6, 11, 12 and 13. Incertain embodiments, M is aluminum, chromium, titanium, indium, gallium,zinc cobalt, or copper. In certain embodiments, M is aluminum. In otherembodiments, M is chromium.

In certain embodiments, M has an oxidation state of +2. In certainembodiments, M is Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II),Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In certain embodiments M isZn(II). In certain embodiments M is Cu(II).

In certain embodiments, M has an oxidation state of +3. In certainembodiments, M is Al(III), Cr(III), Fe(III), Co(III), Ti(III) In(III),Ga(III) or Mn(III). In certain embodiments M is Al(III). In certainembodiments M is Cr(III).

In certain embodiments, M has an oxidation state of +4. In certainembodiments, M is Ti(IV) or Cr(IV).

In certain embodiments, M¹ and M² are each independently a metal atomselected from the periodic table groups 2-13, inclusive. In certainembodiments, M is a transition metal selected from the periodic tablegroups 4, 6, 11, 12 and 13. In certain embodiments, M is aluminum,chromium, titanium, indium, gallium, zinc cobalt, or copper. In certainembodiments, M is aluminum. In other embodiments, M is chromium. Incertain embodiments, M¹ and M² are the same. In certain embodiments, M¹and M² are the same metal, but have different oxidation states. Incertain embodiments, M¹ and M² are different metals.

In certain embodiments, one or more of M¹ and M² has an oxidation stateof +2. In certain embodiments, M¹ is Zn(II), Cu(II), Mn(II), Co(II),Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In certainembodiments M¹ is Zn(II). In certain embodiments M¹ is Cu(II). Incertain embodiments, M² is Zn(II), Cu(II), Mn(II), Co(II), Ru(II),Fe(II), Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In certain embodimentsM² is Zn(II). In certain embodiments M² is Cu(II).

In certain embodiments, one or more of M¹ and M² has an oxidation stateof +3. In certain embodiments, M¹ is Al(III), Cr(III), Fe(III), Co(III),Ti(III) In(III), Ga(III) or Mn(III). In certain embodiments M¹ isAl(III). In certain embodiments M¹ is Cr(III). In certain embodiments,M² is Al(III), Cr(III), Fe(III), Co(III), Ti(III) In(III), Ga(III) orMn(III). In certain embodiments M² is Al(III). In certain embodiments M²is Cr(III).

In certain embodiments, one or more of M¹ and M² has an oxidation stateof +4. In certain embodiments, M¹ is Ti(IV) or Cr(IV). In certainembodiments, M² is Ti(IV) or Cr(IV).

In certain embodiments, one or more neutral two electron donorscoordinate to M M¹ or M² and fill the coordination valence of the metalatom. In certain embodiments, the neutral two electron donor is asolvent molecule. In certain embodiments, the neutral two electron donoris an ether. In certain embodiments, the neutral two electron donor istetrahydrofuran, diethyl ether, acetonitrile, carbon disulfide, orpyridine. In certain embodiments, the neutral two electron donor istetrahydrofuran. In certain embodiments, the neutral two electron donoris an epoxide. In certain embodiments, the neutral two electron donor isan ester or a lactone.

Enumerated Embodiments

The following enumerated embodiments are representative of some aspectsof the invention.

1. A method for the integrated production of chemicals comprising thesteps of:

-   -   a) in a first reaction zone, contacting an epoxide in the        presence of a carbonylation catalyst with a syngas stream        containing hydrogen and carbon monoxide thereby causing carbon        monoxide in the industrial gas stream to react with the epoxide        to provide an epoxide carbonylation product,    -   b) removing an upgraded gas stream from the first reaction zone        wherein the upgraded gas stream has a higher hydrogen to carbon        monoxide than the starting syngas stream,    -   c) in a second reaction zone, utilizing the upgraded gas stream        to conduct a second chemical process requiring a hydrogen to CO        ratio higher than the ratio in the industrial gas stream        utilized in step (a).        2. The method of embodiment 1, wherein the syngas stream has a        molar hydrogen to CO ratio between 0.5:1 and 1.2:1 and the        upgraded gas stream has a hydrogen to CO ratio of at least        1.9:1.        3. The method of embodiment 1, wherein the second chemical        process comprises Fischer Tropsch synthesis.        4. The method of embodiment 1, wherein the second chemical        process comprises reaction on a fuel cell.        5. The method of embodiment 1, wherein the second chemical        process comprises hydrogenation.        6. The method of embodiment 1, wherein the epoxide carbonylation        product is selected from the group consisting of: optionally        substituted beta lactone, optionally substituted succinic        anhydride, and a polyester resulting from alternating        polymerization of CO and the epoxide.        7. The method of embodiment 1, wherein the epoxide is ethylene        oxide.        8. The method of embodiment 7, wherein the carbonylation product        is beta propiolactone.        9. The method of embodiment 7, wherein the epoxide carbonylation        product is succinic anhydride and the upgraded gas stream has a        molar hydrogen to CO ratio greater than 5:1.        10. The method of embodiment 9, wherein and the upgraded gas        stream has a hydrogen to CO ratio greater than 10:1, greater        than 20:1, greater than 50:1, greater than 100:1, or greater        than 1,000:1.        11. The method of embodiment 9, wherein the upgraded gas stream        is substantially free of carbon monoxide.        12. Beta-propiolactone produced by carbonylation of ethylene        oxide having a pMC of zero, as defined by ASTM D6866, using        carbon monoxide having a pMC greater than zero, as defined by        ASTM D6866.        13. Beta-propiolactone produced by carbonylation of ethylene        oxide having a pMC greater than zero, as defined by ASTM D6866,        using carbon monoxide having a pMC of zero, as defined by ASTM        D6866.        14. The beta-propiolactone of embodiment 12 wherein the carbon        monoxide has a pMC of 107.5.        15. The beta-propiolactone of embodiment 13 wherein the ethylene        oxide has a pMC of 107.5.        16. Beta-propiolactone produced by carbonylation of ethylene        oxide using carbon monoxide, wherein one of the ethylene oxide        and carbon monoxide has a biobased content greater than zero        percent, and the other has a biobased content of less than 100        percent.        17. The beta-propiolactone of embodiment 16 wherein the ethylene        oxide has a biobased content of 100%.        18. The beta-propiolactone of embodiment 16 wherein the carbon        monoxide has a biobased content of 100%.        19. A process for producing beta-propiolactone having biobased        content greater than zero percent and less than 100 percent        comprising carbonylating ethylene oxide using carbon monoxide,        wherein one of the ethylene oxide and carbon monoxide has a        biobased content greater than zero percent, and the other has a        biobased content of less than 100 percent.        20. A method for determining whether a sample of        beta-propiolactone was produced from a combination of bio-based        and fossil carbon synthons, comprising the steps of:    -   (i) thermally decomposing the sample to ethylene and carbon        dioxide;    -   (ii) determining the isotopic abundance of ¹⁴C in the carbon        dioxide carbon;    -   (iii) determining the isotopic abundance of ¹⁴C in the ethylene        carbons;        wherein, if the isotopic abundances in (ii) and (iii) are not        equal, the beta-propiolactone was produced from a combination of        bio-based and fossil carbon synthons.        21. Succinic anhydride produced by carbonylation of ethylene        oxide having a pMC of zero, as defined by ASTM D6866, using        carbon monoxide having a pMC greater than zero, as defined by        ASTM D6866.        22. Succinic anhydride produced by carbonylation of ethylene        oxide having a pMC greater than zero, as defined by ASTM D6866,        using carbon monoxide having a pMC of zero, as defined by ASTM        D6866.        23. The succinic anhydride of embodiment 21 wherein the carbon        monoxide has a pMC of 107.5.        24. The succinic anhydride of embodiment 22 wherein the ethylene        oxide has a pMC of 107.5.        25. Succinic anhydride produced by carbonylation of ethylene        oxide using carbon monoxide, wherein one of the ethylene oxide        and carbon monoxide has a biobased content greater than zero        percent, and the other has a biobased content of less than 100        percent.        26. The succinic anhydride of embodiment 25 wherein the ethylene        oxide has a biobased content of 100%.        27. The succinic anhydride of embodiment 25 wherein the carbon        monoxide has a biobased content of 100%.        28. A process for producing succinic anhydride having biobased        content greater than zero percent and less than 100 percent        comprising carbonylating ethylene oxide using carbon monoxide,        wherein one of the ethylene oxide and carbon monoxide has a        biobased content greater than zero percent, and the other has a        biobased content of less than 100 percent.        29. A method for determining whether a sample of succinic        anhydride was produced from a combination of bio-based and        fossil carbon synthons, comprising the steps of:    -   (i) thermally decomposing the sample to γ-ketopimelic acid and        carbon dioxide;    -   (ii) determining the isotopic abundance of ¹⁴C in the carbon        dioxide carbon;    -   (iii) determining the isotopic abundance of ¹⁴C in the        γ-ketopimelic acid carbons;        wherein, if the isotopic abundances in (ii) and (iii) are not        equal, the succinic anhydride was produced from a combination of        bio-based and fossil carbon synthons.        30. A method for determining whether a sample of polyacrylic        acid was produced from a combination of bio-based and fossil        carbon synthons, comprising the steps of:    -   (i) thermally decomposing the sample in the presence of a copper        catalyst at a temperature between 103° C. and 216° C. to carbon        dioxide and a residue;    -   (ii) determining the isotopic abundance of ¹⁴C in the carbon        dioxide carbon;    -   (iii) determining the isotopic abundance of ¹⁴C in the residue;

wherein, if the isotopic abundances in (ii) and (iii) are not equal, thepolyacrylic acid was produced from a combination of bio-based and fossilcarbon synthons.

31. Beta propiolactone, wherein the beta propiolactone has three carbonatoms, and wherein two of the three carbon atoms in the betapropiolactone are bio-based and the third carbon atom is fossil-based.32. The beta propiolactone of embodiment 31, wherein the carbonyl carbonof the beta propiolactone is fossil-based.33. Beta propiolactone, wherein the beta propiolactone has three carbonatoms, and wherein one of the three carbon atoms in the betapropiolactone is bio-based and the other two carbons atom arefossil-based.34. The beta propiolactone of embodiment 33, wherein the carbonyl carbonof the beta propiolactone is bio-based.35. Succinic anhydride, wherein the succinic anhydride has four carbonatoms, and wherein two of the four carbon atoms of the succinicanhydride are bio-based and two of the carbon atoms are fossil-based.36. The succinic anhydride of embodiment 35, wherein the two carbonylcarbon atoms of the succinic anhydride are bio-based.37. The succinic anhydride of embodiment 35, wherein the two carbonylcarbon atoms of the succinic anhydride are fossil-based.

It is to be understood that the embodiments of the invention hereindescribed are merely illustrative of the application of the principlesof the invention. Reference herein to details of the illustratedembodiments is not intended to limit the scope of the claims, whichthemselves recite those features regarded as essential to the invention.

What is claimed is:
 1. Beta-propiolactone produced by carbonylation ofethylene oxide having a pMC of zero, as defined by ASTM D6866, usingcarbon monoxide having a pMC greater than zero, as defined by ASTMD6866.
 2. Beta-propiolactone produced by carbonylation of ethylene oxidehaving a pMC greater than zero, as defined by ASTM D6866, using carbonmonoxide having a pMC of zero, as defined by ASTM D6866.
 3. Thebeta-propiolactone of claim 1, wherein the carbon monoxide has a pMC of107.5.
 4. The beta-propiolactone of claim 2, wherein the ethylene oxidehas a pMC of 107.5.
 5. Beta-propiolactone produced by carbonylation ofethylene oxide using carbon monoxide, wherein one of the ethylene oxideand carbon monoxide has a biobased content greater than zero percent,and the other has a biobased content of less than 100 percent.
 6. Thebeta-propiolactone of claim 5, wherein the ethylene oxide has a biobasedcontent of 100%.
 7. The beta-propiolactone of claim 5, wherein thecarbon monoxide has a biobased content of 100%.
 8. A method forproducing beta-propiolactone having biobased content greater than zeropercent and less than 100 percent, the method comprising carbonylatingethylene oxide using carbon monoxide, wherein one of the ethylene oxideand carbon monoxide has a biobased content greater than zero percent,and the other has a biobased content of less than 100 percent.
 9. Amethod for determining whether a sample of beta-propiolactone wasproduced from a combination of bio-based and fossil carbon synthons,comprising: (i) thermally decomposing the sample to ethylene and carbondioxide; (ii) determining the isotopic abundance of ¹⁴C in the carbondioxide carbon; and (iii) determining the isotopic abundance of ¹⁴C inthe ethylene carbons; wherein, if the isotopic abundances in (ii) and(iii) are not equal, the beta-propiolactone was produced from acombination of bio-based and fossil carbon synthons.
 10. Succinicanhydride produced by carbonylation of ethylene oxide having a pMC ofzero, as defined by ASTM D6866, using carbon monoxide having a pMCgreater than zero, as defined by ASTM D6866.
 11. Succinic anhydrideproduced by carbonylation of ethylene oxide having a pMC greater thanzero, as defined by ASTM D6866, using carbon monoxide having a pMC ofzero, as defined by ASTM D6866.
 12. The succinic anhydride of claim 10,wherein the carbon monoxide has a pMC of 107.5.
 13. The succinicanhydride of claim 11, wherein the ethylene oxide has a pMC of 107.5.14. Succinic anhydride produced by carbonylation of ethylene oxide usingcarbon monoxide, wherein one of the ethylene oxide and carbon monoxidehas a biobased content greater than zero percent, and the other has abiobased content of less than 100 percent.
 15. The succinic anhydride ofclaim 14, wherein the ethylene oxide has a biobased content of 100%. 16.The succinic anhydride of claim 14, wherein the carbon monoxide has abiobased content of 100%.
 17. A process for producing succinic anhydridehaving biobased content greater than zero percent and less than 100percent comprising carbonylating ethylene oxide using carbon monoxide,wherein one of the ethylene oxide and carbon monoxide has a biobasedcontent greater than zero percent, and the other has a biobased contentof less than 100 percent.
 18. A method for determining whether a sampleof succinic anhydride was produced from a combination of bio-based andfossil carbon synthons, comprising: (i) thermally decomposing the sampleto γ-ketopimelic acid and carbon dioxide; (ii) determining the isotopicabundance of ¹⁴C in the carbon dioxide carbon; and (iii) determining theisotopic abundance of ¹⁴C in the γ-ketopimelic acid carbons; wherein, ifthe isotopic abundances in (ii) and (iii) are not equal, the succinicanhydride was produced from a combination of bio-based and fossil carbonsynthons.
 19. A method for determining whether a sample of polyacrylicacid was produced from a combination of bio-based and fossil carbonsynthons, comprising: (i) thermally decomposing the sample in thepresence of a copper catalyst at a temperature between 103° C. and 216°C. to carbon dioxide and a residue; (ii) determining the isotopicabundance of ¹⁴C in the carbon dioxide carbon; and (iii) determining theisotopic abundance of ¹⁴C in the residue; wherein, if the isotopicabundances in (ii) and (iii) are not equal, the polyacrylic acid wasproduced from a combination of bio-based and fossil carbon synthons. 20.Beta propiolactone, wherein the beta propiolactone has three carbonatoms, and wherein two of the three carbon atoms in the betapropiolactone are bio-based and the third carbon atom is fossil-based.21. The beta propiolactone of claim 20, wherein the carbonyl carbon ofthe beta propiolactone is fossil-based.
 22. Beta propiolactone, whereinthe beta propiolactone has three carbon atoms, and wherein one of thethree carbon atoms in the beta propiolactone is bio-based and the othertwo carbons atom are fossil-based.
 23. The beta propiolactone of claim22, wherein the carbonyl carbon of the beta propiolactone is bio-based.24. Succinic anhydride, wherein the succinic anhydride has four carbonatoms, and wherein two of the four carbon atoms of the succinicanhydride are bio-based and two of the carbon atoms are fossil-based.25. The succinic anhydride of claim 24, wherein the two carbonyl carbonatoms of the succinic anhydride are bio-based.
 26. The succinicanhydride of claim 24, wherein the two carbonyl carbon atoms of thesuccinic anhydride are fossil-based.